Herbicidal substituted aryl-haloalkylpyrazoles

ABSTRACT

The invention herein relates to certain substituted-arylpyrazole compounds, herbicidal compositions containing same, herbicidal methods of use and processes for preparing said compounds.

RELATED APPLICATIONS

This application is a division of application Ser. No. 07/763,762, filedSep. 25, 1991, now U.S. Pat. No. 5,281,571, which is aContinuation-in-Part of application Ser. No. 07/600,031, filed Oct. 18,1990, now abandoned.

FIELD OF THE INVENTION

The field of the invention contemplated herein pertains to herbicidalcompounds generically defined by the above title, to compositionscontaining same and processes for preparing said compounds.

BACKGROUND OF THE INVENTION

Various substituted 3-aryl- and 5-arylpyrazole type compounds are knownin the literature. Such compounds have various utilities, e.g., aschemical intermediates, pharmaceuticals and herbicides.

Among the substituted 3-aryl-5-(halo)alkylpyrazoles and5-aryl-3-(halo)alkylpyrazoles in the art are those having a variety ofsubstituent radicals on the aryl and/or pyrazole moieties of thecompound, e.g., alkyl, carboxyl, alkoxycarbonyl, formyl, phenyl andphenyl substituted with various groups such as alkyl, halo or nitrogroups, etc. For example, compounds of this type are known wherein thearyl moiety is a substituted or unsubstituted phenyl radical, in whichthe substituent radicals are alkyl, cycloalkyl, alkaryl, halogen,trifluoromethyl, etc., and the pyrazolyl radical is substituted invarious positions on the nitrogen or carbon atoms with alkyl, halogen,alkoxy, hetero-cycles, S(O)_(n) R members, wherein n is 0-2 and R may bea variety of radicals such as those substituted on the aryl or pyrazolemoieties.

Compounds of the above type having utility as herbicides, typicallyrequire application rates as high as five or ten or more kilograms perhectare to achieve adequate weed control. Accordingly, it is an objectof this invention to provide a novel class of arylpyrazole-typecompounds having uniquely high phytotoxic unit activity against aspectrum of weeds, including narrow-leaf and broadleaf weeds yetmaintain a high degree of safety in a plurality of crops, especiallysmall grains and/or row crops such as wheat, barley, corn, soybeans,peanuts, etc.

The 1-(halo)alkyl-3-(substituted)aryl-4-halo-5-haloalkylpyrazoles and1-(halo)alkyl-5-(substituted)-aryl-4-halo-3-haloalkylpyrazoles describedherein are new.

SUMMARY OF THE INVENTION

This invention relates to herbicidally-active compounds, compositionscontaining these compounds, processes for making them and herbicidalmethods of using the same.

The herbicidal compounds of this invention are characterized by thestructure of Formula I ##STR1## and agriculturally-acceptable salts andhydrates thereof wherein R₁ is independently C₁₋₈ alkyl; C₃₋₈cycloalkyl, cycloalkenyl, cycloalkylalkyl, or cycloalkenylalkyl; C₂₋₈alkenyl or alkynyl; benzyl; wherein the above members may be optionallysubstituted with halogen, amino, nitro, cyano, hydroxy, alkoxy,alkylthio, ##STR2## YR₁₀, or NR₁₁ R₁₂ ; R₂ is C₁₋₅ haloalkyl;

R₃ is halogen;

R₄ is an R₁ member, thioalkyl, alkoxyalkyl or polyalkoxyalkyl, carbamyl,halogen, amino, nitro, cyano, hydroxy, C₁₋₁₀ heterocycle containing 1-4O, S(O)_(m) and/or NR₁₈ hetero atoms, C₆₋₁₂ aryl, aralkyl or alkaryl,##STR3## YR₁₅ or NR₁₆ R₁₇ group. Any two R₄ groups may be combinedthrough a saturated and/or unsaturated carbon, --(C═X)--, and/or heteroO, S(O)_(m) and/or NR₁₈ linkage to form a cyclic ring having up to 9ring members which may be substituted with any of the R₄ members;

X is O, S (O)_(m), NR₁₉ or CR₂₀ R₂₁ ;

Y is O, S(O)_(m) or NR₂₂ ;

R₈₋₂₂ are hydrogen or one of the R₄ members;

m is 0-2 and

n is 1-5.

A preferred subgenus of the substituted-arylpyrazolyl compounds in thisinvention are those according to Formula II ##STR4## andagriculturally-acceptable salts and hydrates thereof wherein R₁ is C₁₋₅alkyl, alkylthio, alkoxyalkyl, C₂₋₄ alkenyl, benzyl, which members mayoptionally be substituted with halogen, amino, nitro, cyano, hydroxy or##STR5## groups; R₂, R₃, X, Y and R₈ are as defined for Formula I;

R₅ is halogen or hydrogen;

R₆ and R₇ are as defined for the R₄ member of Formula I.

Particularly preferred compounds of this invention are those accordingto Formula III ##STR6## and agriculturally-acceptable salts and hydratesthereof wherein R₁ is C₁₋₅ alkyl;

R₂, R₃ and R₅ are as previously defined;

R₆ is halogen, nitro, cyano, YR₁₀ ;

R₇ is hydrogen or an R₄ member and

R₆ and R₇ are combined through a saturated and/or unsaturated carbon,--(C═X)--, and/or hetero O, S(O)_(m) and/or NR₁₈ linkage to form acyclic ring having up to 9 ring members which may be substituted withany of the R₄ members, provided that when said linkage contains ##STR7##said cyclic ring has at least six ring members and X, Y, R₁₈ and m areas previously defined.

Still more preferred are compounds according to Formula III andagriculturally-acceptable salts and hydrates thereof wherein

R₁ is methyl;

R₂ is CF₃, CF₂ Cl or CF₂ H;

R₃ is chloro or bromo;

R₅ is fluoro;

R₆ is chloro;

R₇ is propargyloxy, allyloxy, polyalkoxy, OCH(R₂₃)COR₂₄ where R₂₃ ishydrogen, methyl or ethyl and R₂₄ is YR₁₀ or NR₁₁ R₁₂ ;

R₆ and R₇ are combined through an --OCH₂ (C═O)N(R₁₈)-linkage to give afused six member ring and

Y, R₁₀ -R₁₂ and R₁₈ are as previously defined.

Preferred species according to this invention include the following:

4-Chloro-3-(4-chloro-2-fluoro-5-propargyloxyphenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole,

2-(2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorophenoxy)propanoicacid, ethyl ester,

(2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorophenoxy)aceticacid, 1-methylethyl ester,

4-Chloro-3-(4-chloro-2-fluoro-5-(methoxymethoxy)phenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole,

4-Chloro-3-(4-chloro-2-fluoro-5-(methoxyethoxy)phenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole,

(2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorophenoxy)aceticacid, 1,1-dimethylethyl ester,

(2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorophenoxy)aceticacid,

2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorobenzoicacid, 2-ethoxy-1-methyl-2-oxoethyl ester,

2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorobenzoicacid, 2-methoxy-1-methyl-2-oxoethyl ester,

2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorobenzoicacid, ethyl ester,

2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorobenzoicacid, 1-methylethyl ester and

6-(4-Chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-7-fluoro-4-(2-propynyl)-2H-1,4-benzoxazin-3-(4H)-one.

While all of the above compounds have exhibited particularly efficacioususe in a plurality of crops, tests to date indicate that those of mostpreferred interest are the Compound Nos. 135, 137, 261, 282 and 446.These compounds collectively provide outstanding control of resistantbroadleaf weeds such as pigweed, cocklebur, velvetleaf and hemp sesbaniain various crops such as corn, soybean and nuts and in forestry againsttrees and vines. Other of the compounds of this invention exhibitexcellent herbicidal effect against weeds in other crops such as wheatand barley.

Some of the compounds of the present invention may have more than onepossible stereoisomer and these stereoisomers may differ in herbicidalefficacy. The structures illustrated are intended to include allpossible stereoisomers.

The above compounds may be suitably applied in a variety of applicationmodes, e.g., pre-emergent and/or postemergent, surface applied,pre-plant incorporated, etc.

Another aspect of this invention relates to processes for preparing thecompounds according to Formulae I-III and their precursors,intermediates and/or starting materials. These process aspects will bediscussed in more detail below.

Other aspects of this invention relate to herbicidal compositionscontaining the compounds of Formulae I-III and to herbicidal methods ofusing those compositions to control undesirable weeds.

It is further within the purview of this invention that thesubstituted-arylpyrazole compounds of Formulae I-III be formulated incompositions containing other herbicidal compounds as co-herbicides,e.g., acetamides, esp., acetanilides, thiocarbamates, ureas,sulfonylureas, sulfonamides, imidazolinones, benzoic acid and itsderivatives, diphenyl ethers, salts of glyphosate, etc.

Other additaments may be included in such herbicidal formulations asdesired and appropriate, e.g, antidotes (safeners) for the herbicide(s),plant disease control agents, such as fungicides, insecticides,nematicides and other pesticides.

As used herein, the terms "alkyl", "alkenyl", alkynyl" when used eitheralone or in compound form, e.g., haloalkyl, haloalkenyl, alkoxy,alkoxyalkyl, etc., are intended to embrace linear or branched-chainmembers. Preferred alkyl members are the lower alkyls having from 1 to 4carbon atoms and preferred alkenyl and alkynyl members are those havingfrom 2 to 4 carbon atoms.

The term "haloalkyl" is intended to mean alkyl radicals substituted withone or more halogen (chloro, bromo, iodo or fluoro) atoms; preferredmembers of this class are those having from 1 to 4 carbon atoms,especially the halomethyl radicals, e.g., trifluoromethyl. Inpolyhaloalkyl members, the halogens can all be the same or mixedhalogens.

Representative, non-limiting alkyl, alkenyl, alkynyl, cycloalkyl,cycloalkylalkyl, cycloalkenyl and cycloalkenylalkyl members include thefollowing:

Methyl, ethyl, the isomeric propyls, butyls, pentyls, hexyls, heptyls,octyls, nonyls, decyls, etc.; vinyl, allyl, crotyl, methallyl, theisomeric butenyls, pentenyls, hexenyls, heptenyls, octenyls; ethynyl,the isomeric propynyls, butynyls, pentynyls, hexynyls, etc.; the alkoxy,polyalkoxy, alkoxyalkyl and polyalkoxyalkyl analogs of the foregoingalkyl groups, e.g., methoxy, ethoxy, propoxys, butoxys, pentoxys andhexoxys and corresponding polyalkoxys and alkoxyalkyls, e.g.,methoxymethoxy, methoxyethoxy, ethoxymethoxy, ethoxy-ethoxy,methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, propoxymethyl,isopropoxymethyl, butoxymethyl, isobutoxymethyl, tertbutoxymethyl,pentoxymethyl, hexoxymethyl, etc., cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclopropylmethyl, cyclobutylmethyl,cyclopentylmethyl, etc.; the isomeric cyclopentenes, cyclohexenes andcycloheptenes having mono- or di-unsaturation; representative aryl,aralkyl and alkaryl groups include phenyl, the isomeric tolyls andxylyls, benzyl, naphthyl, etc.

Representative mono-, di- and tri- haloalkyl members include:chloromethyl, chloroethyl, bromomethyl, bromoethyl, iodomethyl,iodoethyl, chloropropyl, bromopropyl, iodopropyl, 1,1,-dichloromethyl,1,1-dibromomethyl, 1,1-dichloropropyl, 1,2-dibromopropyl,2,3-dibromopropyl, 1-chloro-2-bromoethyl, 2-chloro-3-bromopropyl,trifluoromethyl, trichloromethyl, etc.

Representative heterocyclic members include: alkylthiodiazolyl;piperidyl; piperidylalkyl; dioxolanylalkyl, thiazolyl; alkylthiazolyl;benzothiazolyl; halobenzothiazolyl; furyl; alkyl-substituted furyl;furylalkyl; pyridyl; alkylpyridyl; alkyloxazolyl; tetrahydrofurylalkyl;3-cyanothienyl; thienylalkyl; alkyl-substituted thienyl;4,5-polyalkylene-thienyl; piperidinyl; alkylpiperidinyl; pyridyl; di- ortetrahydropyridinyl; alkyltetrahydromorpholyl; alkylmorpholyl;azabicyclononyl; diazabicycloalkanyl, benzoalkylpyrrolidinyl;oxazolidinyl; perhydrooxazolidinyl; alkyloxazolidyl; furyloxazolidinyl,thienyloxazolidinyl, pyridyloxazolidinyl, pyrimidinyloxazolidinyl,benzooxazolidinyl, C₃₋₇ spirocycloalkyloxazolidinyl, alkylaminoalkenyl;alkylideneimino; pyrrolidinyl; piperidonyl; perhydroazepinyl;perhydroazocinyl; pyrazolyl; dihydropyrazolyl; piperazinyl;perhydro-1,4-diazepinyl; quinolinyl, isoquinolinyl; di-, tetra- andperhydroquinolyl-- or -- isoquinolyl; indolyl and di- andperhydroindolyl and said heterocyclic members substituted with radicalssuch as defined in Formulae I-III.

By "agriculturally-acceptable salts" of the compounds defined by theabove formulae is meant a salt or salts which readily ionize in aqueousmedia to form a cation or anion of said compounds and the correspondingsalt anion or cation, which salts have no deleterious effect on theherbicidal properties of a given herbicide and which permit formulationof various mixtures, e.g., herbicide-antidote compositions without undueproblems of mixing, suspension, stability, applicator equipment use,packaging, etc.

By "herbicidally-effective" is meant the amount of herbicide required toeffect a meaningful injury or destruction to a significant portion ofaffected undesirable plants or weeds. Although of no hard and fast rule,it is desirable from a commercial viewpoint that 80-85% or more of theweeds be destroyed, although commercially significant suppression ofweed growth can occur at much lower levels, particularly with some verynoxious, herbicide-resistant plants.

DETAILED DESCRIPTION OF THE INVENTION

The compounds according to this invention are suitably prepared by avariety of processes as will be described below.

In broad aspect, the preferred overall process for preparing thecompounds of Formulae I-III is best viewed in the separate process stepsrequired to get the necessary intermediates, immediate precursors andend products of the above formulae. The products of "Process I" providethe intermediates necessary for "Processes II-XVI". The productsaccording to Formulae I-III are prepared by either a single process"II-XVI" or any combination of "Processes II-XVI". It is expresslyunderstood that various modifications obvious to those skilled in theart are contemplated. Specific embodiments are described in Examples1-42 below.

In the sequence of process steps described below, the various symbolsdefining radical substituents, e.g., R₁ -R₂₄, X, Y, etc. have the samemeanings as defined for the compounds of Formulae I-III, unlessotherwise qualified or limited.

Process I

This process describes the preparation of important intermediatecompounds of Formula B, or isomeric mixtures thereof, which are usefulin the overall process scheme for producing compounds of Formulae I-III.##STR8##

The process for the preparation of a compound of Formula B suitablyproceeds from compounds of Formula A. Compounds of Formula A areprepared by known means from substituted acetophenones, which also areknown in the art; the structure shown for Formula A is meant to embodyall possible tautomeric forms or mixtures thereof. Compounds of FormulaA can be prepared in any anhydrous solvent or mixture of solvents; thepreferred solvents are ether, alcohols, dimethylsulfoxide, toluene,benzene, etc., by reacting a substituted acetophenone in the presence ofan ester with a strong base such as an alkali alkoxide, alkali amide oralkali hydride with alkali alkoxides such as sodium methoxide beingpreferred. Reaction temperature is in the range of -100° C. to 200° C.,preferably -78° C. to 50° C. The reaction period may be chosen from therange of a few minutes to several weeks depending on the amounts ofreagents, reaction temperature, etc. After completion of the reaction,the compound of Formula A is isolated by diluting the reaction mixturewith water, which may be followed by acidification of the aqueous layeror, alternatively, by diluting the reaction mixture with aqueous acid.Subsequently, the product is isolated by a method such ascrystallization or solvent extraction. If necessary, the product ispurified by standard methods. The cyclization of this intermediate togive compounds of Formula B can be carried out in any suitable solventby treatment with hydrazine or substituted hydrazines withalkylhydrazines being preferred. Reaction temperature is in the range of-78° C. to 200° C., preferably 10° C. to 120° C. The reaction period maybe chosen from the range of a few minutes to several weeks depending onthe amounts of reagents, reaction temperature, etc. The product isisolated after completion of the reaction by filtration and/orconcentration of the reaction mixture. If necessary, the product ispurified by standard methods such as extraction, crystallization, columnchromatography, etc.

In the case of the addition of hydrazine to compounds of Formula A, theresultant pyrazole of Formula C may be treated with an alkylating agentto obtain compounds of Formula B. In this case, products of Formula Bcan be obtained by treatment of the above compound with an alkylatingagent such as methyl iodide, benzyl bromide, allyl bromide,dimethylsulfate, etc. The preferred solvents are toluene,dimethylsulfoxide, acetone, dimethylformamide, dioxane, etc. Thereaction may be carried out with or without a base. In cases in which abase is employed, alkali metal carbonates or hydroxides such as sodiumcarbonate or sodium hydroxide may be used. Reaction temperature is inthe range of -78° C. to 200° C., preferably 10° C. to 120° C. Thereaction period may be chosen from the range of a few minutes to severalweeks depending on the amounts of reagents, reaction temperature, etc.The product is isolated after completion of the reaction by filtrationand/or concentration of the reaction mixture. If necessary, the productis purified by standard methods such as extraction, crystallization,column chromatography, etc. ##STR9##

Compounds illustrated by Formula C can exist in two possible tautomericforms, either a 5-arylpyrazole or a 3-arylpyrazole. The 5-arylpyrazoledepicted in Formula C is meant to include both possible tautomericforms. Table 1 shows typical examples of compounds of Formula C.

In all tables herein, boiling points and melting points are measured indegrees Centigrade (° C) and unless otherwise indicated refractiveindices are at 25° C.

                  TABLE 1                                                         ______________________________________                                        PHYSICAL DATA FOR 1-H-5-ARYLPYRAZOLES                                          ##STR10##                                                                    Compound                               physical data                          No.     R.sub.2  R.sub.3                                                                             R.sub.5                                                                           R.sub.6                                                                             R.sub.7                                                                             (mp, °C.)                       ______________________________________                                        1       CF.sub.3 H     H   F     H     114.5-116.5                            2       CF.sub.3 H     Cl  F     H     116.5-117.5                            3       CF.sub.2 Cl                                                                            H     F   Cl    OCH.sub.3                                                                           177.0                                  4       CF.sub.2 CF.sub.3                                                                      H     F   Cl    OCH.sub.3                                                                           135.0                                  5       CF.sub.3 H     F   H     F     156.0-157.0                            6       CF.sub.3 H     F   F     H     157.0-158.0                            7       CF.sub.3 H     H   Cl    H     150.0-151.0                            8       CF.sub.2 Cl                                                                            H     H   Cl    H     148.5-150.0                            9       CF.sub.3 H     F   Cl    OCH.sub.3                                                                           209.0-210.0                            10*     CF.sub.3 Cl    F   Cl    OCH.sub.3                                                                           186.0                                  11      CF.sub.3 H     F   Cl    H     152.0-154.0                            12      CF.sub.2 H                                                                             H     F   H     F     146.0                                  13      CF.sub.3 H     F   Cl    CH.sub.3                                                                            159.0-160.0                            14      CF.sub.3 H     F   OCH.sub.3                                                                           H     138.0                                  ______________________________________                                         *Compound No. 10 was prepared from Compound No. 9 by Process II.         

The 2-fluoro-4-chloro-5-methoxyacetophenone, used to prepare compoundNos. 3, 4 and 9 by the above process, was prepared from2-chloro-4-fluoroanisole, which can be obtained from2-chloro-4-fluorophenol by methods known in the art (C. A. Buehler andD. E. Pearson, Survey of Organic Synthesis, pages 285-382,Wiley-Interscience, New York, 1970). Treatment of2-chloro-4-fluoroanisole with titanium tetrachloride anddichloromethylmethylether at room temperature gives2-fluoro-4-chloro-5-methoxybenzaldehyde. The2-fluoro-4-chloro-5-methoxybenzaldehyde is converted to2-fluoro-4-chloro-5-methoxyacetophenone by treatment with methylGrignard followed by oxidation using standard methods known in the art.

The above mentioned 2-fluoro-4-chloro-5-methoxyacetophenone and itsanalogous precursor, 2-fluoro-4-chloro-5-methoxybenzaldehyde andprocesses for preparing them are the discovery of other inventors (BruceC. Hamper and Kindrick L. Leschinsky) employed by the assignee herein.

Tables 2 and 3 show typical examples of compounds prepared by Process I.

                                      TABLE 2                                     __________________________________________________________________________    PHYSICAL DATA FOR 1-ALKYL-5-ARYLPYRAZOLES                                      ##STR11##                                                                    Compound                   physical data                                      No.   R.sub.1                                                                              R.sup.2                                                                           R.sup.5                                                                         R.sup.6                                                                           R.sup.7                                                                           (mp; nD)                                           __________________________________________________________________________    15    CH.sub.3                                                                             CF.sub.3                                                                          Cl                                                                              Cl  H   85.0° C.                                    16    CH(CH.sub.3).sub.2                                                                   CF.sub.3                                                                          F Cl  OCH.sub.3                                                                         75.0° C.                                    17    CF.sub.2 H                                                                           CF.sub.3                                                                          F Cl  OCH.sub.3                                                                         76.0° C.                                    18    CH.sub.3                                                                             CF.sub.3                                                                          H NO.sub.2                                                                          H   116.5-121.0° C.                             19    CH.sub.3                                                                             CF.sub.3                                                                          H NO.sub.2                                                                          OCH.sub.3                                                                         105.0-107.0° C.                             20    CH.sub.3                                                                             CF.sub.3                                                                          F H   F   38.0-39.0° C.                               21    CH.sub.3                                                                             CF.sub.3                                                                          F F   H   37.0-38.0° C.                               22    CH.sub.3                                                                             CF.sub.3                                                                          H Cl  H   26.6-28.3° C.                               23    CH.sub.3                                                                             CF.sub.2 Cl                                                                       H Cl  H   31.0-32.0° C.                               24    CH.sub.3                                                                             CF.sub.3                                                                          F Cl  OCH.sub.3                                                                         119.5° C.                                   25    CH.sub.2 CH.sub.3                                                                    CF.sub.3                                                                          F Cl  OCH.sub.3                                                                         84.0° C.                                    26    CH.sub.2 CO.sub.2 CH.sub.3                                                           CF.sub.3                                                                          F Cl  OCH.sub.3                                                                         98.5° C.                                    27    CH.sub.3                                                                             CF.sub.3                                                                          H OCH.sub.3                                                                         NO.sub.2                                                                          140.0° C.                                   28    CH.sub.3                                                                             CF.sub.3                                                                          Cl                                                                              Cl  F   nD; 1.5221 (25° C.)                         29    CH.sub.3                                                                             CF.sub.3                                                                          F Cl  H   70.0-72.0° C.                               30    CH.sub.3                                                                             CF.sub.2 H                                                                        F H   F   83.0° C.                                    31    n-butyl                                                                              CF.sub.3                                                                          F Cl  OCH.sub.3                                                                         nD; 1.5068 (25° C.)                         32    n-propyl                                                                             CF.sub.3                                                                          F Cl  OCH.sub.3                                                                         78.0° C.                                    33    benzyl CF.sub.3                                                                          F Cl  OCH.sub.3                                                                         viscous oil                                        34    allyl  CF.sub.3                                                                          F Cl  OCH.sub.3                                                                         58.0° C.                                    35    CH.sub.3                                                                             CF.sub.3                                                                          F Cl  CH.sub.3                                                                          50.0-52.0° C.                               __________________________________________________________________________

                                      TABLE 3                                     __________________________________________________________________________    PHYSICAL DATA FOR 1-ALKYL-3-ARYLPYRAZOLES                                      ##STR12##                                                                    Compound                    physical data                                     No.   R.sub.1                                                                              R.sup.2                                                                            R.sup.5                                                                         R.sup.6                                                                           R.sup.7                                                                           (mp, nD)                                          __________________________________________________________________________    36    CH.sub.3                                                                             CF.sub.3                                                                           Cl                                                                              Cl  H   45.0° C.                                   37    CH.sub.3                                                                             CF.sub.3                                                                           F OCH.sub.3                                                                         H   nD 1.5139 (25° C.)                         38    CH.sub.3                                                                             CF.sub.3                                                                           Cl                                                                              F   H   Clear oil                                         39    CH.sub.3                                                                             CF.sub.3                                                                           H NO.sub.2                                                                          H   101.0-103.0° C.                            40    CH.sub.3                                                                             CF.sub.3                                                                           F H   F   nD 1.4925 (25° C.)                         41    CH.sub.3                                                                             CF.sub.3                                                                           F Cl  OCH.sub.3                                                                         121.0° C.                                  42    CH.sub.3                                                                             CF.sub.3                                                                           F F   H   51° C.                                     43    CH.sub.3                                                                             CF.sub.3                                                                           H Cl  H   55.5-57.5° C.                              44    CH.sub.3                                                                             CF.sub.2 Cl                                                                        H Cl  H   39.3-40.1° C.                              45    Et     CF.sub.3                                                                           F Cl  OCH.sub.3                                                                         73.5° C.                                   46    CH.sub.3                                                                             CF.sub.3                                                                           H OCH.sub.3                                                                         NO.sub.2                                                                          133.0° C.                                  47    CH.sub.3                                                                             CF.sub.3                                                                           Cl                                                                              Cl  F   35.0-38.0° C.                              48    CH.sub.3                                                                             CF.sub.3                                                                           F Cl  H   45.0-47.0° C.                              49    CH.sub.3                                                                             CF.sub.2 H                                                                         F H   F   48.0-49.0° C.                              50    CH.sub.3                                                                             CF.sub.3                                                                           F Cl  CH.sub.3                                                                          48.0-49.0° C.                              51    CH.sub.2 CO.sub.2 CH.sub.3                                                           CF.sub.3                                                                           F Cl  OCH.sub.3                                                                         116.5° C.                                  52    n-butyl                                                                              CF.sub.3                                                                           F Cl  OCH.sub.3                                                                         42.0° C.                                   53    n-propyl                                                                             CF.sub.3                                                                           F Cl  OCH.sub.3                                                                         72.0° C.                                   54    CH(CH.sub.3).sub.2                                                                   CF.sub.3                                                                           F Cl  OCH.sub.3                                                                         69.5° C.                                   55    CF.sub.2 H                                                                           CF.sub.3                                                                           F Cl  OCH.sub.3                                                                         116.5° C.                                  56    benzyl CF.sub.3                                                                           F Cl  OCH.sub.3                                                                         69.0° C.                                   57    allyl  CF.sub.3                                                                           F Cl  OCH.sub.3                                                                         55.0° C.                                   58    CH.sub.3                                                                             CF.sub.2 H                                                                         F Cl  CH.sub.3                                                                          42.0-43.0° C.                              59    CH.sub.3                                                                             CF.sub.2 CF.sub.3                                                                  F Cl  OCH.sub.3                                                                         84.0-85.0° C.                              60    CH.sub.3                                                                             CF.sub.2 Cl                                                                        F Cl  OCH.sub.3                                                                         73.0-74.0°  C.                             61    CH.sub.3                                                                             CF.sub.3                                                                           H F   H   clear oil                                         __________________________________________________________________________

Process II

In this process description, one class of products according to FormulaI wherein R₃ is halogen is prepared by the halogenation of thecorresponding compound of Formula B. In this process, R₁ can be aspreviously defined and further include hydrogen. ##STR13##

Any inert solvent may be used in this reaction that does not markedlyhinder the reaction from proceeding or the reaction may be carried outneat. Such solvents include, but are not limited to, organic acids,inorganic acids, hydrocarbons, halogenated hydrocarbons, aromatichydrocarbons, ethers and sulfides, sulfoxides or sulfones. Halogenatingagents suitable for the above reaction include bromine, chlorine,N-bromosuccinimide, N-chlorosuccinimide, sulfuryl chloride, etc. Withsome halogenating agents it is preferable to use an organic peroxide orlight as a catalyst. The amount of halogenating agent can range fromless than one molar equivalent to an excess. Reaction temperature is inthe range of -100° C. to 200° C., preferably.10° C. to 100° C. Thereaction period may be chosen from the range of a few minutes to severalweeks depending on the amounts of reagents, reaction temperature, etc.After completion of the reaction the product is isolated by diluting thereaction mixture with water and the product is isolated by a method suchas crystallization or solvent extraction. If necessary, the product ispurified by standard methods.

Process III

This section describes a process for the preparation of compoundsaccording to Formula D (a Formula I compound in which one of the R₄residues is a nitro group) starting with compounds according to FormulaI. ##STR14##

Nitrating agents such as concentrated nitric acid, fuming nitric acid,mixtures of nitric acid with concentrated sulfuric acid, alkyl nitratesand acetyl nitrate are suitable for this reaction. Solvents such asmineral acids, organic acids, organic solvents, such as acetic anhydrideor methylene chloride, and water or mixtures of these solvents may beused. The nitrating agent may be used in equimolar amounts or in excess.Reaction temperature is in the range of -100° C. to 200° C., preferably-10° C. to 100° C. The reaction period may be chosen from the range of afew minutes to several days depending on the amounts of reagents,reaction temperature, etc. After completion of the reaction the productis isolated by diluting the reaction mixture with water and the productis isolated by methods such as crystallization or solvent extraction. Ifnecessary, the product is purified by standard methods.

Process IV

In this process description, one class of products according to FormulaF (one species of Formula II compounds) is prepared by displacement ofthe Z radical of the corresponding compound of Formula E, wherein Z isany suitable leaving group of the previously defined R₄ members.##STR15##

Formation of products of Formula F can be carried out by treatment ofcompounds of Formula E with an alkoxide, thioalkoxide, amine, etc., oran alcohol, mercaptan, amine, etc., in the presence of a base in anysuitable solvent or mixture of solvents. The preferred solvents aredimethylsulfoxide, acetone, dimethylformamide, dioxane, water, etc. ormixtures of solvents including two phase mixtures (such as water andmethylene chloride or other organic solvent). The base may be an organicbase (such as a trialkylamine or another organic amine) or an inorganicbase (an alkali carbonate such as potassium carbonate or sodiumcarbonate or an alkali metal hydroxide such as sodium hydroxide). In thecase of two immiscible liquid phases, it may be advantageous to add aphase transfer catalyst such as a benzyltrialkylammonium halide or otherammonium salt. Reaction temperature is in the range of -100° C. to 200°C., preferably -10° C. to 100° C. The reaction period may be chosen fromthe range of a few minutes to several weeks depending on the amounts ofreagents, reaction temperature, etc. The product is isolated aftercompletion of the reaction by filtration and/or concentration of thereaction mixture. If necessary, the product is purified by standardmethods such as extraction, crystallization, column chromatography, etc.

Process V

In this process description, compounds of Formula I are prepared fromcompounds of Formula G (Formula I compounds in which one of the R₄members is a nitro residue). ##STR16##

A. In the first step of this two step process, compounds according toFormula G are reduced to give a derivative according to Formula Iwherein one of the R₄ radicals is an amine group. Reducing agentssuitable in an acidic medium include, but are not limited to, metalssuch as iron, zinc, or tin. The reaction solvent can include eitherorganic or inorganic acids, such as acetic acid or hydrochloric acid,and may be used as concentrated acid solutions or dilute aqueoussolutions. Reaction temperature is in the range of 0° C. to 200° C.,preferably 10° C. to 120° C. The reaction period may be chosen from therange of a few minutes to several weeks depending on the amounts ofreagents, reaction temperature, etc.

After completion of the reaction the product is isolated by diluting thereaction mixture with water and the product is isolated by a method suchas crystallization or solvent extraction. If necessary, the product ispurified by standard methods.

Alternatively, compounds of Formula G may be reduced by catalytichydrogenation. For catalytic hydrogenation, which may be carried out atatmospheric or elevated pressures, suitable catalysts include Raneynickel, palladium-carbon, palladium black, palladium on any suitablesupport, palladium oxide, platinum, platinum black, etc. Solventsinclude any inert solvent which does not markedly hinder the reactionincluding alcohols, ethers, etc. The product is isolated aftercompletion of the reaction by filtration and concentration of thereaction mixture. If necessary, the product is purified by standardmethods such as extraction, crystallization, column chromatography, etc.

B. The amine radical of the product of step A can be converted to avariety of functional groups, e.g., a halogen (preferred), cyano,hydroxyl, etc. In the case of conversion of the amine radical to ahalogen, a solution or slurry of the product of step A is treated withcopper salts including cupric halides, cuprous halides, mixtures ofcupric and cuprous halides or other copper salts and their mixtures andwith an alkyl nitrite or organic nitrite such as t-butylnitrite. In thisreaction any suitable solvent may be employed, although, anhydroussolvents such as anhydrous acetonitrile are preferred. Reactiontemperature is in the range of 0° C. to 200° C., preferably 10° C. to100° C. The reaction period may be chosen from the range of a fewminutes to several weeks depending on the amounts of reagents, reactiontemperature, etc. The product is isolated after completion of thereaction by filtration and/or concentration of the reaction mixture. Ifnecessary, the product is purified by standard methods such asextraction, crystallization, column chromatography, etc.

Alternative process operations for converting the amine radical tovarious functional groups, including those mentioned in the precedingparagraph include use of various conventional procedures, e.g., theSandmeyer, Meerwein, etc., reactions which employ diazonium salts asintermediates.

Process VI

In this process description, compounds according to Formula I, whereinone of the R₄ members is YH, are prepared from compounds according toFormula I wherein one of the R₄ members is YR₁₅ and R₁₅ is not hydrogen.

The reaction can be carried out as a solution or suspension in anysuitable solvent or neat. A Lewis acid such as, but not limited to,BBr₃, AlCl₃, etc., or inorganic or organic acids such as concentrated oraqueous hydrochloric acid, sulfuric acid, hydrobromic acid, acetic acid,etc., can be employed. Alternatively, nucleophilic reagents fordealkylation may be employed including trimethylsilyl iodide, cyanidesalts, mercaptide salts, alkali metal halides, etc. Reaction temperatureis in the range of 0° C. to 200° C., preferably 10° C. to 100° C. Thereaction period may be chosen from the range of a few minutes to severalweeks depending on the amounts of reagents, reaction temperature, etc.The product is isolated after completion of the reaction by filtrationand/or concentration of the reaction mixture. If necessary, the productis purified by standard methods such as extraction, crystallization,column chromatography, etc.

Process VII

In this process description, compounds according to Formula I (whichincludes Formulae II and III compounds), wherein one of the R₄ membersis YR₁₅ and R₁₅ is not hydrogen, are prepared from compounds accordingto Formula I wherein one of the R₄ members is YH or NR₁₆ R₁₇.

In representative embodiments of this process, formation of productsdefined above can be carried out by treatment of the starting materialwith an alkylating agent such as an alkyl halide or alkyl sulfonate,e.g., methyl iodide, allyl bromide, propargyl bromide, methylphenylsulfonate, etc., or an acylating agent. The reaction may becarried out in any suitable solvent or mixture of solvents, with orwithout a catalyst, in the presence or absence of a base. The preferredsolvents are dimethylsulfoxide, acetone, dimethylformamide, dioxane,etc., or mixtures of solvents including two phase mixtures (such aswater and methylene chloride or other organic solvent). In the case oftwo immiscible liquid phases, it may be advantageous to add a phasetransfer catalyst such as a benzyltrialkylammonium halide or otherammonium salt. The base may be an organic base (such as a trialkylamineor another organic amine) or an inorganic base (an alkali carbonate ormetal, such as potassium or sodium carbonate or sodium hydroxide).Reaction temperature is in the range of 0° C. to 200° C., preferably 10°C. to 100° C. The reaction period may be chosen from the range of a fewminutes to several weeks depending on the amounts of reagents, reactiontemperature, etc. The product is isolated after completion of thereaction by filtration and/or concentration of the reaction mixture. Ifnecessary, the product is purified by standard methods such asextraction, crystallization, column chromatography, etc.

Process VIII

This process describes the preparation of compounds of Formula K(Formula II compounds wherein R₇ is YCH_(2-p) (R₂₅)_(p) COYR₂₇) from thecorresponding compounds of Formula H. The radicals R₂₅₋₂₇ are aspreviously defined for the said R₄ members; the Y members areindependently as previously defined and p is an integer from 0 to 2.##STR17##

A. In the first step of this two step process, compounds of Formula Hare converted to compounds of Formula J by hydrolysis of the YR₂₆radical. The reaction can be carried out in any suitable solvent ormixture of solvents, with or without a catalyst, in the presence of abase or acid. The preferred solvents are water, alcohols, dioxane,dimethylsulfoxide, acetic acid, acetone, dimethylformamide, etc. In thecase of base hydrolysis, inorganic bases such as alkali hydroxides arepreferred. For acid hydrolysis, inorganic acids such as concentratedhydrochloric acid or sulfuric acid, organic acids or mixtures of suchacids may be employed. Reaction temperature is in the range of about 0°C. to 200° C., preferably 10° C. to 100° C. The reaction period may bechosen from the range of a few minutes to several weeks depending on theamounts of reagents, reaction temperature, etc. After completion of thereaction the product is isolated by diluting the reaction mixture withwater and/or treating the solution with acid (in the case of basehydrolysis) and the product is isolated by a method such ascrystallization or solvent extraction. If necessary, the product ispurified by-standard methods.

B. The last step of this process is meant to include the transformationof compounds of Formula J to compounds of Formula K by any of thevariety of standard techniques for the preparation of derivatives ofcarboxylic acids. This process step is an esterification or anamide-forming reaction. The esterification can be carried out by usingan excess of the alcohol corresponding to the objective ester in thepresence of a mineral acid (e.g., sulfuric acid). The amide derivativescan be prepared by treating compounds of Formula J with the desiredamine either neat or in a suitable solvent. The esterification oramide-forming reactions can also be carried out in the presence of aninert solvent and a dehydrating agent.

Alternatively, the product of step A can be converted to an acid halideor anhydride and treated with an alcohol or amine. Preparation of theacid halide is carried out in the presence of a halogenating agent suchas, but not limited to, thionyl chloride, phosphorus pentachloride,oxalyl chloride, etc., with or without an inert solvent. Any inertsolvent which does not interfere with the reaction may be employed. Acatalytic amount of an amine base such as triethylamine, pyridine ordimethylformamide or the like may be added for the purpose of promotingthis reaction. The reaction temperature is in the range of -20° C. tothe boiling point of the solvent used. The reaction period ranges fromseveral minutes to 48 hours depending upon the amounts of reactants usedand the reaction temperature. After completion of the reaction, theexcess halogenating reagent and solvent(s) are removed from the reactionproduct by evaporation or distillation. The resultant acid halide may besubjected to an amine or alcohol directly or purified by the usualmeans.

The acid halide is treated with an alcohol or amine to give a compoundof Formula K. The reaction can be carried out in the absence of asolvent, in the presence of an inert solvent or with a mixture ofsolvents including two phase mixtures (such as water and methylenechloride or other organic solvent). A base such as triethylamine,pyridine, alkali metal hydroxide and/or a catalytic amount of a phasetransfer catalyst such as a benzyltrialkylammonium halide or otherammonium salt may be added for the purpose of promoting this reaction.The reaction temperature is in the range of -20° C. to the boiling pointof the solvent used. The reaction period ranges from several minutes to48 hours depending upon the amounts of reactants used and the reactiontemperature. The product is isolated after completion of the reaction byfiltration and/or concentration of the reaction mixture. If necessary,the product is purified by standard methods such as extraction,crystallization, column chromatography, etc.

Compounds required as starting materials for Processes IX through XI areobtained by the above Processes II-VIII.

Process IX

In this process description, compounds according to Formula N areprepared from compounds according to Formula L (Formula II compoundswherein R₆ is YCH_(2-q) (R₂₈)_(q) COOR₂₉, R₇ is a nitro radical, Y is aspreviously defined, q is an integer from 0 to 2 and radicals R₂₈₋₃₀ areas previously defined for the said R₄ members), as described below.##STR18##

A. In the first step of this two step process, compounds according toFormula L are converted to compounds of Formula M by reduction of thenitro radical to an amine radical and subsequent cyclization. By choiceof the reaction conditions, one can obtain either the uncyclized amine(Formula L compounds wherein the nitro radical is substituted by anamine radical) or the cyclized product. Typically, reaction conditionsare chosen such that the cyclized product is obtained directly.Alternatively, the uncyclized amine can be isolated by standard methodsand cyclized to give compounds of Formula M in a separate step usingstandard conditions. Reducing agents suitable in an acidic mediuminclude, but are not limited to, metals such as iron, zinc or tin. Thereaction solvent can include either organic or inorganic acids, such asacetic acid or hydrochloric acid, and may be used as concentrated acidsolutions or dilute aqueous solutions. Reaction temperature is in therange of 0° C. to 200° C., preferably 10° C. to 120° C. The reactionperiod may be chosen from the range of a few minutes to several weeksdepending on the amounts of reagents, reaction temperature, etc.

After completion of the reaction the product is separated by dilutingthe reaction mixture with water and isolated by a method such ascrystallization or solvent extraction. If necessary, the product ispurified by standard methods.

Alternatively, compounds of Formula L may be reduced by catalytichydrogenation. For catalytic hydrogenation, which may be carried out atnormal or elevated pressures, suitable catalysts include Raney nickel,palladium-carbon, palladium black, palladium on any suitable support,palladium oxide, platinum, platinum black, etc. Solvents include anyinert solvent which does not markedly hinder the reaction includingalcohols, ethers, etc. By choice of the reaction conditions, one canobtain either the uncyclized amine (Formula L compounds wherein thenitro radical is substituted by an amine radical) or the cyclizedproduct. Typically, reaction conditions are chosen such that thecyclized product is obtained directly. Alternatively, the uncyclizedamine can be isolated by standard methods and cyclized to give compoundsof Formula M in a separate step using standard conditions. The productis isolated after completion of the reaction by filtration andconcentration of the reaction mixture. If necessary, the product ispurified by standard methods such as extraction, crystallization, columnchromatography, etc.

B. In this step the product of step A is converted to compounds ofFormula N. Formation of products defined above can be carried out bytreatment of compounds of Formula M with an alkylating agent such as analkyl halide or alkyl sulfonate, e.g., methyl iodide, allyl bromide,propargyl bromide, methyl phenylsulfonate, etc., or an acylating agent.The reaction may be carried out in any suitable solvent or mixture ofsolvents, with or without a catalyst, in the presence or absence of abase. The preferred solvents are dimethylsulfoxide, acetone,dimethylformamide, dioxane, etc., or mixtures of solvents including twophase mixtures (such as water and methylene chloride or other organicsolvent). In the case of two immiscible liquid phases, it may beadvantageous to add a phase transfer catalyst such as abenzyltrialkylammonium halide or other ammonium salt. The base may be anorganic base (such as a trialkylamine or another organic amine) or aninorganic base such as potassium or sodium carbonate or hydroxide.Reaction temperature is in the range of 0° C. to 200° C., preferably 10°C. to 120° C. The reaction period may be chosen from the range of a fewminutes to several weeks depending on the amounts of reagents, reactiontemperature, etc. The product is isolated after completion of thereaction by filtration and/or concentration of the reaction mixture. Ifnecessary, the product is purified by standard methods such asextraction, crystallization, column chromatography, etc.

Process X

In this process description, compounds according to Formula Q whereinR₃₃ is not hydrogen are prepared from compounds according to Formula O(Formula II compounds wherein R₆ is a nitro radical, R₇ is YCH_(2-r)(R₃₁)_(r) COOR₃₂, Y is as previously defined, r is an integer from 0 to2 and radicals R₃₁₋₃₃ are as previously defined for the said R₄ members.##STR19##

A. In the first step of this two step process, compounds according toFormula O are converted to compounds of Formula P by reduction of thenitro radical to an amine radical and subsequent cyclization. By choiceof the reaction conditions, one can obtain either the uncyclized amine(Formula O compounds wherein the nitro radical is substituted by anamine radical) or the cyclized product. Typically, reaction conditionsare chosen such that the cyclized product is obtained directly.Alternatively, the uncyclized amine can be isolated by standard methodsand cyclized to give compounds of Formula P in a separate step usingstandard conditions. Reducing agents suitable in an acidic mediuminclude, but are not limited to, metals such as iron, zinc or tin. Thereaction solvent can include either organic or inorganic acids, such asacetic acid or hydrochloric acid, and may be used as concentrated acidsolutions or dilute aqueous solutions. Reaction temperature is in therange of 0° C. to 200° C., preferably 10° C. to 120° C. The reactionperiod may be chosen from the range of a few minutes to several weeksdepending on the amounts of reagents, reaction temperature, etc.

After completion of the reaction the product is separated by dilutingthe reaction mixture with water and isolated by a method such ascrystallization or solvent extraction. If necessary, the product ispurified by standard methods.

Alternatively, compounds of Formula O may be reduced by catalytichydrogenation. For catalytic hydrogenation, which may be carried out atnormal or elevated pressures, suitable catalysts include Raney nickel,palladium-carbon, palladium black, palladium on any suitable support,palladium oxide, platinum, platinum black, etc. Solvents include anyinert solvent which does not markedly hinder the reaction includingalcohols, ethers, etc. By choice of the reaction conditions, one canobtain either the uncyclized amine (Formula O compounds wherein thenitro radical is substituted by an amine radical) or the cyclizedproduct. Typically, reaction conditions are chosen such that thecyclized product is obtained directly. Alternatively, the uncyclizedamine can be isolated by standard methods and cyclized to give compoundsof Formula P in a separate step using standard conditions. The productis isolated after completion of the reaction by filtration andconcentration of the reaction mixture. If necessary, the product ispurified by standard methods such as extraction, crystallization, columnchromatography, etc.

B. In this step the product of step A is converted to compounds ofFormula Q wherein R₃₃ is not hydrogen. Formation of products definedabove can be carried out by treatment of compounds of Formula P with analkylating agent such as an alkyl halide or alkyl sulfonate, e.g.,methyl iodide, allyl bromide, propargyl bromide, methyl phenylsulfonate,etc., or an acylating agent. The reaction may be carried out in anysuitable solvent or mixture of solvents, with or without a catalyst, inthe presence or absence of a base. The preferred solvents aredimethylsulfoxide, acetone, dimethylformamide, dioxane, etc. The basemay be an organic base (such as a trialkylamine or another organicamine) or an inorganic base such as potassium or sodium carbonate orhydroxide. Reaction temperature is in the range of 0° C. to 200° C.,preferably 10° C. to 120° C. The reaction period may be chosen from therange of a few minutes to several weeks depending on the amounts ofreagents, reaction temperature, etc. The product is isolated aftercompletion of the reaction by filtration and/or concentration of thereaction mixture. If necessary, the product is purified by standardmethods such as extraction, crystallization, column chromatography, etc.

Process XI

This section describes a process for the preparation of compoundsaccording to Formula S from compounds of Formula R (Formula II compoundswherein R₆ is an amino radical, R₇ is YC(R₃₄)_(s) CCR₃₅, Y is aspreviously defined, s is an integer from 0 to 2 and the radicals R₃₄₋₃₆are any of the previously defined R₄ members). ##STR20##

The process for the preparation of compounds of Formula S suitablyproceeds from compounds of Formula R. In this reaction any suitablesolvent may be employed, although anhydrous solvents such as anhydrousacetonitrile are preferred. A solution or slurry of a compound ofFormula R is treated with copper salts including cupric halides, cuproushalides, mixtures of cupric and cuprous halides or other copper saltsand their mixtures and with an alkyl nitrite or organic nitrite such ast-butylnitrite. Reaction temperature is in the range of 0° C. to 200°C., preferably 10° C. to 100° C. The reaction period may be chosen fromthe range of a few minutes to several weeks depending on the amounts ofreagents, reaction temperature, etc. The product is isolated aftercompletion of the reaction by filtration and/or concentration of thereaction mixture. If necessary, the product is purified by standardmethods such as extraction, crystallization, column chromatography, etc.

Process XII

This process describes the preparation of compounds of Formulae U, V, W,X, Y or Z (Formula II compounds in which the R₇ substituent is alkyl,substituted alkyl, haloalkyl, carboxaldehyde, carboxylic acid or acarboxylic acid derivative such as the previously defined CXYR₈ or CXR₉)from compounds of Formula T. The radicals R₃₇ and R₃₈ are as previouslydefined for the R₄ members and X₁ and X₂ are halogens. Processschematics are shown below. ##STR21##

In the first step of this process, compounds of Formula T are convertedto either compounds of Formula U or W or a mixture of these products.Any inert solvent may be used in this reaction that does not markedlyhinder the reaction from proceeding. Such solvents include, but are notlimited to, organic acids, inorganic acids, hydrocarbons, halogenatedhydrocarbons, aromatic hydrocarbons, ethers, sulfoxides or sulfones.Halogenating agents suitable for the above reaction include bromine,chlorine, N-bromosuccinimide, N-chlorosuccinimide, sulfuryl chloride,etc. With some halogenating agents it is preferable to use an organicperoxide or light as a catalyst. The amount of halogenating agent canrange from less than one molar amount to an excess. Reaction temperatureis in the range of -78° C. to 200° C., preferably 10° C. to 120° C. Thereaction period may be chosen from the range of a few minutes to severalweeks depending on the amounts of reagents, reaction temperature, etc.After completion of the reaction the product or products are isolated bydiluting the reaction mixture with water and the product(s) are isolatedby a method such as crystallization or solvent extraction. If necessary,the product(s) are purified by standard methods.

Compounds of Formula U can be converted to compounds of Formula V bydisplacement of the halogen radical X₁ by a suitable nucleophile.Formation of products of Formula V can be carried out by treatment ofcompounds of Formula U with an alkoxide, thioalkoxide, cyanide, amine,alkyl or aryl anion, etc., or an alcohol, mercaptan, amine, etc., in thepresence of a base in any suitable solvent or mixture of solvents. Thepreferred solvents are dimethyl-sulfoxide, acetone, dimethylformamide,dioxane, water, etc., or mixture of solvents including two-phasemixtures (such as water and methylene chloride or other organicsolvent). The base may be an organic base (such as a trialkylamine oranother organic amine) or an inorganic base (an alkali carbonate such aspotassium carbonate or sodium carbonate or an alkali metal hydroxidesuch as sodium hydroxide). In the case of two immiscible liquid phases,it may be advantageous to add a phase transfer catalyst such as abenzyltrialkylammonium halide or other ammonium salt. Reactiontemperature is in the range of -78° C. to 200° C., preferably 10° C. to120° C. The reaction period may be chosen from the range of a fewminutes to several weeks depending on the amounts of reagents, reactiontemperature, etc. The product is isolated after completion of thereaction by filtration and/or concentration of the reaction mixture. Ifnecessary, the product is purified by standard methods such asextraction, crystallization, column chromatography, etc.

Formation of products of Formula X can be carried out by acid hydrolysisof compounds of Formula W. To effect acid hydrolysis, compounds ofFormula W are subjected to an excess of a mineral acid such ashydrochloric acid or sulfuric acid, with excess of sulfuric acid beingpreferred. Reaction temperature is in the range of 0° C. to the boilingpoint of the inert solvent, preferably 10° C. to 100° C. The reactionperiod may be chosen from the range of a few minutes to several weeksdepending on the amounts of reagents, reaction temperature, etc. Aftercompletion of the reaction the product or products are separated bydiluting the reaction mixture with water and are isolated by a methodsuch as crystallization or solvent extraction. If necessary, theproduct(s) are purified by standard methods.

Compounds of Formula Y are obtained by oxidation of Formula X compounds.Any suitable inert solvent may be employed in this reaction includinghydrocarbons, aromatic hydrocarbons, pyridine and its derivatives,water, etc. Oxidizing agents employed include, but are not limited to,potassium permanganate or potassium dichromate. Reaction temperature isin the range of -50° C. to the boiling point of the inert solvent,preferably 10° C. to 100° C. The reaction period may be chosen from therange of a few minutes to several weeks depending on the amounts ofreagents, reaction temperature, etc. After completion of the reactionthe product or products are separated by diluting the reaction mixturewith water and isolated by a method such as crystallization or solventextraction. If necessary, the product(s) are purified by standardmethods.

The last step of this process is meant to include the transformation ofcompounds of Formula Y to compounds of Formula Z by any of the varietyof standard techniques for preparation of derivatives of carboxylicacids. This process step is an esterification or an amide-formingreaction. This may be accomplished directly from compound of Formula Yor via an alkali metal salt of compound of Formula Y. The esterificationcan be carried out by using an excess of the alcohol corresponding tothe objective ester in the presence of a mineral acid (e.g., sulfuricacid). The amide derivatives can be prepared by treating compound ofFormula Y with the desired amine either neat or in a suitable solvent.The esterification or amide-forming reactions can also be carried out inthe presence of an inert solvent and a dehydrating agent.

Alternatively, compounds of Formula Y can be converted to an acid halideor anhydride and treated with an alcohol or amine. Preparation of theacid halide is carried out in the presence of a halogenating agent suchas, but not limited to, thionyl chloride, phosphorus pentachloride,oxalyl chloride, etc., with or without an inert solvent. Any inertsolvent which does not interfere with the reaction may be employed. Acatalytic amount of an amine base such as triethylamine, pyridine ordimethylformamide or the like may be added for the purpose of promotingthis reaction. The reaction temperature is in the range of -20° C. tothe boiling point of the solvent used. The reaction period ranges fromseveral minutes to 48 hours depending upon the amounts of reactants usedand the reaction temperature. After completion of the reaction, theexcess halogenating reagent and solvent(s) are removed from the reactionproduct by evaporation or distillation. The acid halide is treated withan alcohol or amine to give a compound of Formula Z. The reaction can becarried out in the absence of a solvent, in the presence of an inertsolvent or with a mixture of solvents including two phase mixtures (suchas water and methylene chloride or other organic solvent). A base suchas triethylamine, pyridine, alkali metal and/or a catalytic amount of aphase transfer catalyst such as a benzyltrialkylammonium halide or otherammonium salt may be added for the purpose of promoting this reaction.The reaction temperature is in the range of -20° C. to the boiling pointof the solvent used. The reaction period ranges from several minutes to48 hours depending upon the amounts of reactants used and the reactiontemperature. The product is isolated after completion of the reaction byfiltration and/or concentration of the reaction mixture. If necessary,the product is purified by standard methods such as extraction,crystallization, column chromatography, etc.

Process XIII

This section describes a process for the preparation of compoundsaccording to Formula I in which one of the R₄ residues is a thiol group(Formula AA) starting with compounds according to Formula I. ##STR22##

In this process, the desired compounds are obtained by preparation of ahalosulfonyl intermediate followed by reduction to give compounds ofFormula AA. Any solvent may be employed that does not hinder theprogress of the reaction such as halogenated hydrocarbons, ethers,alkylnitriles, mineral acids, etc. An excess of chlorosulfonic acid ispreferred as both the reagent and solvent for the formation ofchlorosulfonyl intermediates. The reaction temperature is in the rangeof 25° C. to the boiling point of the solvent employed. The reactionperiod may be chosen from the range of a few minutes to several weeksdepending on the amounts of reagents, reaction temperature, etc. Aftercompletion of the reaction the product or products are isolated bydiluting the reaction mixture with water and the product(s) are isolatedby a method such as crystallization or solvent extraction. If necessary,the product(s) are purified by standard methods.

Reduction of the halosulfonyl intermediate can be carried out in organicor inorganic acids, such as acetic acid or hydrochloric acid, ormixtures of these acids in inert solvents. Reducing agents suitable inan acidic medium include, but are not limited to, metals such as iron,zinc or tin. Reaction temperature is in the range of 0° C. to 150° C.,preferably 10° C. to 120° C. The reaction period may be chosen from therange of a few minutes to several weeks depending on the amounts ofreagents, reaction temperature, etc.

After completion of the reaction the product is isolated by diluting thereaction mixture with water and the product is isolated by a method suchas crystallization or solvent extraction. If necessary, the product ispurified by standard methods.

Process XIV

This section describes a process for the preparation of compoundsaccording to Formula I in which one of the R₄ residues is a cyclic(thio)ketal or (thio)acetal radical (Formula CC) starting with compoundsaccording to Formula BB. ##STR23##

R₃₉ is hydrogen or a previously-defined R₄ member; A and B areindependently O or S and n is an integer from 0 to 2. In this process,the desired compounds of Formula CC are prepared from compounds ofFormula BB by conversion of the carbonyl group to a cyclic (thio)acetalor (thio)ketal group. The aldehyde or ketone group of a compound ofFormula BB is treated with a diol, dithiol or hydroxythiol. Any solventmay be employed that does not hinder the progress of the reaction suchas halogenated hydrocarbons, aromatic hydrocarbons, ethers,alkyl-nitriles, mineral acids, etc. Alternatively, the reaction may becarried out in the absence of a solvent. Typically, the reaction iscarried out in the presence of an acid such as mineral acids, organicacids, etc. The reaction temperature is in the range of 25° C. to theboiling point of the solvent employed. The reaction period may be chosenfrom the range Of a few minutes to several weeks depending on theamounts of reagents, reaction temperature, etc. After completion of thereaction the product or products are isolated by concentration of thereaction mixture and purified by a method such as crystallization orsolvent extraction. If necessary, the product(s) are further purified bystandard methods.

Process XV

This section describes a process for the preparation of compoundsaccording to Formula DD starting with compounds according to Formula BB.##STR24##

R₃₉ -R₄₁ are hydrogen or previously-defined R₄ members. Compounds ofFormula DD are prepared by conversion of the ketone or aldehyde group ofcompounds of Formula BB to an alkene group. This transformation can becarried out by treatment of a compound of Formula BB with a Wittig typereagent such as an alkylidenephosphorane, ylides derived fromphosphonium salts or phosphonate esters, alkylidenesulfuranes, etc.Suitable solvents include, but are not limited to, aromatichydrocarbons, alcohols, alkanes, ethers, halogenated hydrocarbons, etc.The reaction temperature is in the range of -50° C. to the boiling pointof the solvent employed. The reaction period may be chosen from therange of a few minutes to several weeks depending on the amounts ofreagents, reaction temperature, etc. After completion of the reactionthe product or products are isolated by concentration of the reactionmixture and the product(s) are purified by a method such ascrystallization or solvent extraction. If necessary, the product(s) arefurther purified by standard methods.

Process XVI

This section describes a process for the preparation of compoundsaccording to Formula EE starting with compounds according to Formula BB.##STR25##

R₃₉ and R₄₂ are as previously defined for the R₄ members. In thisprocess step, compounds of Formula EE which have an oxime substituent asone of the phenyl radicals are prepared from compounds of Formula BB.The ketone or aldehyde substituent of a compound of Formula BB can beconverted to an oxime by either of two methods. The starting aldehyde orketone of Formula BB can be treated with an O-substituted oxime toafford an oxime of Formula EE. This compound may be further derivatizedby standard methods known by those skilled in the art. Examples of thisapproach include, but are not limited to, treatment of the aldehyde orketone with (aminooxy)acetic acid or other 2-(aminooxy)carboxylic acidsand conversion of the resultant carboxylic acid to any of a number ofcarboxylic acid derivatives such as amides, esters, thioesters, etc.Alternatively, the oxime can be prepared by treatment of compounds ofFormula BB with hydroxylamine or hydroxylamine salts. The resultantoxime can be alkylated to afford derivatives by treatment with analkylating agent such as alkyl halides, alkyl sulfonates, etc. Suitablesolvents for the above reactions include, but are not limited to,aromatic hydrocarbons, alkanes, ethers, alcohols, halogenatedhydrocarbons, etc. The reaction temperature is in the range of -50° C.to the boiling point of the solvent employed. The reaction may becarried out with or without a base. In cases in which a base isemployed, sodium acetate, alkali metal carbonates such as sodiumcarbonate or alkali metal hydroxides such as sodium hydroxide may beused. The reaction period may be chosen from the range of a few minutesto several weeks depending on the amounts of reagents, reactiontemperature, etc. After completion of the reaction the product orproducts are isolated by concentration of the reaction mixture and theproduct(s) are purified by a method such as crystallization or solventextraction. If necessary, the product(s) are further purified bystandard methods.

The following Examples 1-42 describe specific working embodiments forthe preparation of representative compounds according to this invention.

Examples 1 through 4 describe specific working embodiments of Process I.

EXAMPLE 1

This example describes the preparation of3-(2,5-difluorophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole(Compound No. 40) and of5-(2,5-difluorophenyl)-1-methyl-3-(trifluoromethyl)-1H-pyrazole(Compound No. 20).

A. 28.5 g of 2,5-difluoroacetophenone and 26 g of ethyl trifluoroacetatewere stirred in 400 ml of anhydrous ether and cooled in an ice bath. 42ml of 25 wt % sodium methoxide in methanol was then added over 5minutes. After stirring 1 hour at room temperature, the reaction mixturewas extracted with water, the water acidified and extracted withmethylene chloride to give 42 g of1-(2,5-difluorophenyl)-3-(trifluoromethyl)propane-1,3-dione.

B. 34.5 g of1-(2,5-difluorophenyl)-3-(trifluoromethyl)-propane-1,3-dione wasdissolved in 250 ml of acetic acid and 9.5 mL of methylhydrazine slowlyadded. The mixture was heated at 100° C. for 5 minutes then cooled anddiluted with ether. The ether solution was washed with water andpotassium carbonate solution, then dried with magnesium sulfate,filtered and concentrated. The residue was chromatographed to give 9.5 gof 3-(2,5-difluorophenyl)-1-methyl-5-(trifluoro-methyl)-1H-pyrazole.

Anal. Calc. for C₁₁ H₇ N₂ F₅ : C,50.39%; H,2.69%; N,10.68%. Found:C,50.48%; H,2.72%; N,10.64%. and 21.11 g of5-(2,5-difluorophenyl)-1-methyl-3-(trifluoromethyl)-1H-pyrazole (mp38°-39° C.).

Anal. Calc. for C₁₁ H₇ N₂ F₅ : C,50.39%; H,2.69%; N,10.68%. Found:C,50.63%; H,2.65%; N,10.40%.

EXAMPLE 2

This example describes the preparation of5-(2,4-difluorophenyl)-3-(trifluoromethyl)-1H-pyrazole (Compound No. 6).

A. To a solution of 40.0 g (0.256 moles) 2',4'-difluoroacetophenone(commercially available) in 400 mL diethyl ether at 0° C. was added 40mL (0.405 moles) ethyl trifluoroacetate. At 5° C., 80 mL of a 25% wt.sodium methoxide in methanol (0.37 moles) were added over 15 minutes.The reaction mixture was stirred overnight at 25° C. The mixture waspoured over 300 mL ice water and 21.3 mL (0.37 moles) acetic acid wereadded. The organic layer was washed two times with water, dried overanhydrous MgSO₄, and concentrated in vacuo to give 62.85 g (97%)4-(2,4-difluorophenyl)-1,1,1-trifluoro-4-hydroxy-3-buten-2-one as ayellow oil; ¹ HNMR (CDCl₃) ppm: 6.61 (s,1H), 6.87 (m,1H), 6.97 (m,1H),7.97 (m,1H).

Anal. Calc. for C₁₀ H₅ F₅ O₂ ; C,47.64; H, 2.00. Found: C,47.70; H,1.96.

B. At 24° C., 15.0 g (0.06 mole) of the product of step A was dissolvedin 50 mL glacial acetic acid and treated with 2 mL (0.064 mole)anhydrous hydrazine, added over a period of 5 minutes. The reaction washeated to 95° C. for 30 minutes. The reaction was cooled and poured into300 mL ice water. The slurry was filtered and the cake washed with waterand air dried to give 13.86 g (94%) of5-(2,4-difluorophenyl)-3-(trifluoromethyl)-1H-pyrazole as a white solid,mp 157°-158° C.

Anal. Calc. for C₁₀ H₅ F₅ N₂ : C,48.40; H,2.03; N,11.29. Found: C,48.38;H,2.03; N,11.32.

EXAMPLE 3

This example describes the preparation of3-(2,4-difluorophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole(Compound No. 42) and of5-(2,4-difluorophenyl)-1-methyl-3-(trifluoromethyl)-1H-Pyrazole(Compound No. 21).

A slurry of 13.6 g (0.055 mole) of the product of step B, 7.7 g (0.056mole) K₂ CO₃, and 3.7 mL (0.06 mole) methyl iodide in 150 mL acetone wasstirred overnight at 25° C. The solution was diluted with 300 mL coldwater and extracted three times with ethyl acetate. The ethyl acetateextracts were washed with brine, dried over anhydrous MgSO₄, andconcentrated in vacuo. The residue was purified chromatographicallyusing 5% ethyl acetate in hexane as the eluent to give 8.3 g (58%) of3-(2,4-difluorophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole as awhite solid, mp 51° C.

Anal. Calc. for C₁₁ H₇ F₅ N₂ : C,50.39; H,2.69; N,10.68. Found: C,50.36;H,2.70; N,10.70. The chromatography described in the above preparationgave a second fraction which was collected, concentrated and the residuecrystallized to give 4.0 g (28% yield)5-(2,4-difluorophenyl)-1-methyl-3-(trifluoromethyl)-1H-pyrazole as awhite solid, mp 37°-38° C.

Anal. Calc. for C₁₁ H₇ F₅ N₂ : C,50.39; H,2.69; N,10.68. Found: C,50.40;H,2.67; N,10.67.

EXAMPLE 4

This example describes the preparation of3-(2,5-difluorophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole(Compound No. 40).

A solution of 8.5 g (34 mmole) of dry5-(2,5-difluorophenyl)-1H-3-(trifluoromethyl)-1H-pyrazole in 100 mL ofanhydrous toluene was heated to reflux in an apparatus equipped with aDean-Stark trap and treated with 3.25 mL of dimethylsulfate. The mixturewas refluxed for 5 hours, allowed to cool and washed with 10% w/vaqueous NaOH. The organic phase was dried with MgSO₄ and concentrated toafford 7.74 g (86.2%) of a clear, almost colorless oil nD 1.4925 (25°C.).

Anal. Calc. for C₁₁ H₇ N₂ F₅ : C,50.39%; H,2.69%; N,10.68%. Found:C,50.48%; H,2.72%; N,10.64%.

Examples 5 through 7 describe specific working embodiments of ProcessII.

EXAMPLE 5

This example describes the preparation of4-chloro-5-(2,5-difluorophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole(Compound No. 361).

At 25° C., 5.24 g (0.02 mole)3-(2,5-difluorophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole wasdissolved in 40 mL glacial acetic acid and 2.1 g (0.03 mole) chlorinegas was bubbled in over a period of 1 hour. The reaction mixture wasallowed to stir for 2 hours. The reaction solution was poured into 200mL ice water and extracted with ethyl acetate. The organic layer waswashed with water, a saturated NaHCO₃ solution, brine and dried overanhydrous MgSO₄, and stripped in vacuo. The residue was purifiedchromatographically using 3% ethyl acetate in hexane as the eluent togive 5.87 g (99%) of4-chloro-5-(2,5-difluorophenyl)-1-methyl-5-(trifluoro-methyl)-1H-pyrazoleas a light yellow oil n_(D) ²⁵ 1.4977.

Anal. Calc. for C₁₁ H₆ Cl₁ F₅ N₂ : C,44.54; H,2.04; N,9.44; Cl, 11.95.Found: C,44.53; H,2.00; N,9.44; Cl 11.94.

EXAMPLE 6

This example describes the preparation of4-chloro-3-(2,5-difluoro-4-nitrophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole(Compound No. 389).

To 5.00 g of3-(2,5-difluoro-4-nitrophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazoledissolved in 50 ml of acetic acid was added 15 ml of sulfuryl chloride.The mixture was mildly refluxed with 2 ml portions of sulfuryl chlorideadded every 15 minutes. After 6 hours, the mixture was cooled, thendiluted with water and extracted with ether. The ether was washed 3times with water, dried with anhydrous magnesium sulfate, filtered andconcentrated. The residue was chromatographed to give a quantitativeyield of4-chloro-3-(2,5-difluoro-4-nitrophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole.

Anal. Calc. for C₁₁ H₅ N₃ O₂ Cl₁ F₅ : C,38.67%; H,1.48%; N,12.30%.Found: C,38.73%; H,1.48%; N,12.34%.

EXAMPLE 7

This example describes the preparation of4-chloro-3-(4-chloro-2-fluoro-5-methoxyphenyl)-1-(1-methylethyl)-5-(trifluoromethyl)-1H-pyrazole(Compound No. 489).

To a solution of 1.6 g of3-(4-chloro-2-fluoro-5-methoxyphenyl)-1-(1-methylethyl)-5-(trifluoromethyl)-1H-pyrazolein 20 mL of dimethylformamide was added 2.0 g of N-chlorosuccinimide.The solution was heated to 80° C. for 2 hours, allowed to cool andpoured into ice water. The aqueous mixture was extracted three timeswith methylene chloride, the combined organic extracts washed withwater, dried with MgSO₄ and concentrated to give a crude oil. The oilwas purified by chromatography and distilled bulb-to-bulb to afford 1.54g of4-chloro-3-(4-chloro-2-fluoro-5-methoxyphenyl)-1-(1-methylethyl)-5-(trifluoromethyl)-1H-pyrazoleas a yellow oil, nD 1.5192 (24° C.).

Anal. Calc. for C₁₄ H₁₂ N₂ O₁ F₄ Cl₁ : C,45.31%; H,3.26%; N,7.55%.Found: C,45.19%; H,3.27%; N,7.49%.

Examples 8 through 10 describe specific working embodiments of ProcessIII.

EXAMPLE 8

This example describes the preparation of3-(2,5-difluoro-4-nitrophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole(Compound No. 388).

To an ice cooled solution of 50 ml of fuming nitric acid (90%) was addedslowly 8.29 g of3-(2,5-di-fluorophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole. Afteraddition, the mixture was allowed to warm to room temperature and thengently heated to 52° C. Heated for 2.5 hours, then cooled and pouredonto ice. The resulting mixture was extracted with ether and the etherthen washed twice with water, dried with anhydrous magnesium sulfate,filtered and the solvent removed by concentration in vacuo. The residuewas purified utilizing a combination of chromatography andcrystallization to give 5.62 g of3-(2,5-difluoro-4-nitrophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole,mp 80°-81° C.

Anal. Calc. for C₁₁ H₆ N₃ O₂ F₅ : C,43.01%; H,1.97%; N,13.68%. Found:C,42.99%; H,1.97%; N,13.68%.

EXAMPLE 9

This example describes the preparation of4-bromo-3-(2,5-difluoro-4-nitrophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole(Compound No. 396).

At 15° C., 9.5 g (0.03 mole)4-bromo-3-(2,5-difluorophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazolewas slowly added to 100 mL of fuming nitric acid. The reaction warmed to28° C. over a period of 20 minutes. The reaction mixture was stirred at30° C. for 4 hours. The mixture was poured into 500 mL of ice. Afterstirring for 1 hour, the slurry was extracted 3 times with methylenechloride. The methylene chloride extracts were washed with water, driedover anhydrous MgSO₄, and concentrated in vacuo. The residue waspurified chroma-tographically using 10% ethyl acetate in hexane as theeluent to give 5.84 g (55%) of4-bromo-3-(2,5-difluoro-4-nitrophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazoleas a white solid, mp 45.5° C.

Anal. Calc. for C₁₁ H₅ Br₁ F₅ N₃ O₂ : C,34.22; H,1.31; N,10.88. Found:C,34.25; H,1.38; N,10.76.

EXAMPLE 10

This example describes the preparation of4-chloro-3-(2,5-difluoro-4-nitrophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole(Compound No. 389).

A solution of 5.9 g of4-chloro-5-(2,5-difluorophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazolein 6 mL of concentrated H₂ SO₄ was cooled to 15° C. and treated dropwisewith a solution of 1.8 g of 70% HNO₃ in 2 mL of concentrated H₂ SO₄. Thereaction mixture was allowed to stir at 30° C. for 5 hours andsubsequently treated with an additional 1.8 g of 70% HNO₃. Afterstirring overnight at room temperature, the mixture was poured into 250mL of ice water and extracted with methylene chloride. The methylenechloride extract was washed three times with saturated aqueous NaHCO₃,twice with water, dried with MgSO₄ and concentrated in vacuo. Theresultant material was chromatographed through silica using 10% ethylacetate in hexane as the eluant to afford 3.93 g (58%) of4-chloro-3-(2,5-difluoro-4-nitrophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole.

Anal. Calc. for C₁₁ H₅ N₃ O₂ Cl₁ F₅ : C,38.67%, H,1.48%; N,12.30%.Found: C,38.73%; H,1.48%; N,12.34.

Examples 11 through 15 describe specific working embodiments of ProcessIV.

EXAMPLE 11

This example describes the preparation of4-chloro-3-(2-fluoro-5-methoxy-4-nitrophenyl)-1-methyl-5-(trifluoromethyl)-1-pyrazole(Compound No. 390).

5.04 g of4-chloro-3-(2,5-difluoro-4-nitrophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazolewas dissolved in anhydrous ether and the solution cooled with an icebath, then 3.7 ml of a 25 wt. % sodium methoxide in methanol was added.After addition, the ice bath was removed and the mixture stirred for 30minutes at room temperature. The solution was then extracted 4 timeswith water, dried with anhydrous magnesium sulfate, filtered andconcentrated. The residue was chromatographed to give 4.63 g of4-chloro-3-(2-fluoro-5-methoxy-4-nitrophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole,mp 115°-116° C.

Anal. Calc. for C₁₂ H₈ N₃ O₃ Cl₁ F₄ : C,40.75%; H,2.28%; N,11.88%.Found: C,40.84%; H,2.24%; N,11.83%.

EXAMPLE 12

This example describes the preparation of4-chloro-3-(2-fluoro-4-methoxy-5-nitrophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole(Compound No. 387).

At 35° C., 13.7 g (0.04 mole)4-chloro-3-(2,4-difluoro-5-nitrophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole,5.5 g (0.04 mole) K₂ CO₃, and 100 mL methanol were stirred for 1 hour.The reaction was cooled, diluted with 100 mL cold water, and extractedfour times with ethyl acetate. The ethyl acetate extracts were washedwith brine, dried over anhydrous MgSO₄, and stripped in vacuo. Theresidue was purified chromatographically using 25% ethyl acetate inhexane as the eluent to give 13.0 g (90%) of4-chloro-3-(2-fluoro-4-methoxy-5-nitrophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazoleas a white solid, mp 116° C.

Anal. Calc. for C₁₂ H₈ Cl₁ F₄ N₃ O₃ : C,40.75; H,2.28; N,11.88. Found:C,40.74; H,2.34; N,11.90.

EXAMPLE 13

This example describes the preparation of(5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluoro-2-nitrophenyl)thio-aceticacid, ethyl ester (Compound No. 393).

At 25° C., 1.5 g (4.5 Mole)4-chloro-3-(2,5-difluoro-4-nitrophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole,0.69 g (5.0 mmole) K₂ CO₃, 0.55 mL (5.0 mmole) ethyl mercaptoacetate,and 0.05 g (0.5 mmole) CuF₂ were slurried in 15 mL1-methyl-2-pyrrolidinone. The reaction mixture was stirred 28° C. for 24hours. The mixture was cooled, diluted with 100 mL cold water, andextracted four times with ethyl acetate. The ethyl acetate extracts werewashed with brine, dried over anhydrous MgSO₄, and stripped in vacuo.The residue was purified chromato-graphically using 10% diethyl etherand 15% methylene chloride in hexane as the eluent to give 0.86 g (43%)of(5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluoro-2-nitrophenyl)thio-aceticacid, ethyl ester as a yellow solid, mp 79° C.

Anal. Calc. for C₁₅ H₁₂ Cl₁ F₄ N₃ O₄ S₁ : C,40.78; H,2.74; N,9.51;S,7.26. Found: C,40.89; H,2.69; N,9.61; S,7.31.

EXAMPLE 14

This example describes the preparation of5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluoro-N-methyl-2-nitro-N-propylbenzeneamine(Compound No. 402).

At 25° C., 6.83 g (0.02 mole)4-chloro-3-(2,5-difluoro-4-nitrophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole,4.1 g (0.03 mole) K₂ CO₃, 3.1 mL (0.03 mole) N-methyl-N-propylamine anda catalytic amount of CuF₂ were slurried in 50 mL1-methyl-2-pyrrolidinone. The reaction mixture was stirred at 35° C. for2 hours. The mixture was cooled, diluted with 100 mL cold water, andextracted four times with ethyl acetate. The ethyl acetate extracts werewashed with brine, dried over anhydrous MgSO₄, and stripped in vacuo.The residue was purified chromatographically using 15% ethyl acetate inhexane as the eluent to give 6.8 g (86%) of5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluoro-N-methyl-2-nitro-N-propylbenzeneamineas an orange oil, n_(D) ²⁵ 51.5534.

Anal. Calc. for C₁₅ H₁₅ Cl₁ F₄ N₄ O₂ : C,45.64; H,3.83; N,14.19. Found:C,45.52; H,3.87; N, 14.32.

EXAMPLE 15

This example describes the preparation of(4-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-5-fluoro-2-nitrophenoxy)aceticacid, butyl ester (Compound No. 498).

A solution of 3.4 g (0.01 mole)4-chloro-3-(2,4-difluoro-5-nitrophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazoleand 1.4 mL (0.011 mole) butyl glycolate in 25 mL anhydrous THF waschilled to 0° C. Maintaining the temperature below 5° C., 0.33 g (0.011mole) NaH was added in portions. Once the addition was completed, thereaction mixture was allowed to warm to 25° C. After 3 hours the mixturewas carefully quenched with water and extracted with ethyl acetate. Theethyl acetate extracts were washed with brine, dried over anhydrousMgSO₄, and concentrated in vacuo. The residue was purifiedchromatographically with 20% ethyl acetate/hexanes to yield 3.25 g (72%)(4-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-5-fluoro-2-nitrophenoxy)aceticacid, butyl ester as a light yellow solid; mp 65° C.

Anal. Calc. for C₁₇ H₁₆ Cl₁ F₄ N₃ O₅ : C,45.00; H,3.55; N,9.26. Found:C,44.97; H,3.56; N,9.29.

Examples 16 through 19 describe specific working embodiments of ProcessV.

EXAMPLE 16

This example describes the preparation of4-chloro-3-(4-chloro-2-fluoro-5-methoxyphenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole(Compound No. 312).

A. To a solution of 4.05 g of4-chloro-3-(2-fluoro-5-methoxy-4-nitrophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazolein 50 ml of acetic acid was added 1.39 g (0.0249 mol) of iron powder.The reaction mixture was heated near reflux for 2 hours, treated with1.39 g of iron powder, and heated at near reflux for another hour. Aftercooling, concentrating and chromatography, 3.54 g of4-chloro-3-(4-amino-2-fluoro-5-methoxyphenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazolewas isolated.

B. 3.064 g of4-chloro-3-(4-amino-2-fluoro-5-methoxyphenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazolewas dissolved in 50 ml of anhydrous acetonitrile and 1.90 g of anhydrouscupric chloride added. 1.93 ml of t-butyl nitrite (tech., 90%) dissolvedin 10 ml of anhydrous acetonitrile was then added dropwise over 10minutes, stirred an additional 20 minutes and then concentrated. Theresidue was taken up in ethyl acetate, extracted 3 times with 10%aqueous HCl, dried with anhydrous magnesium sulfate, filtered,concentrated and chromatographed to give 2.10 g of4-chloro-3-(4-chloro-2-fluoro-5-methoxyphenyl)-1-methyl-5-(trifluoro-methyl)-1H-pyrazole, mp. 70°-71° C.

Anal. Calc. for C₁₂ H₈ N₂ O₁ Cl₁ F₄ : C,42.01%; H,2.35%; N,8.16%. Found:C,42.15%; H,2.34%; N,8.18%.

EXAMPLE 17

This example describes the preparation of2-chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluoro-N-methyl-N-propylbenzenamine(Compound No. 166).

A. A solution of 5.2 g (0.013 mole)5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluoro-N-methyl-2-nitro-N-propylbenzenaminein 100 mL acetic acid was heated to 80° C. under a nitrogen atmosphere.The heat and nitrogen were removed and 2.2 g (0.039) mole iron powderwas added in 3 portions over 5 min. The solution was stirred at 80° C.for an additional 30 min. The solution was cooled and filtered throughCelite®. The filtrate was diluted with 100 mL water and extracted threetimes with ethyl acetate. The ethyl acetate extracts were washed with asaturated NaHCO₃ solution, dried over anhydrous MgSO₄, and concentratedin vacuo. The residue was purified chromatographically using 30% ethylacetate in hexane as the eluent to give 3.85 g (80%) of5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluoro-N-methyl-N-propyl-1,2-benzenediamineas a light yellow oil, n_(D) ²⁵ 51.5352.

Anal. Calc. for C₁₅ H₁₇ Cl₁ F₄ N₄ : C,49.39; H,4.70; N,15.36. Found:C,49.40; H,4.64; N,15.16.

B. All equipment was flame dried under nitrogen. A solution of 3.35 g(9.2 mmole) of the product of step A in 60 mL acetonitrile at 25° C. wastreated with 0.9 g (9.2 mmole) CuCl and 1.8 g (13.3 mmole) CuCl₂. Asolution of 2.2 mL (18.4 mmole) 90% t-butyl nitrite was added over 5minutes. After 2 hours at 28° C. the reaction mixture was stripped invacuo. The reaction residue was taken up in ethyl acetate and washedthree times with a 10% HCl solution, two times with brine and dried overanhydrous MgSO₄, and concentrated in vacuo. The residue was purifiedchromatographically using 20% ethyl acetate in hexane as the eluent togive 2.45 g (70%) of2-chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluoro-N-methyl-N-propylbenzenamineas a clear colorless oil, n_(D) ²⁵ 1.5030.

Anal. Calc. for C₁₅ H₁₅ C₁₂ F₄ N₃ : C,46.89; H,3.94; N,10.94. Found:C,46.84; H,3.83; N,10.93.

EXAMPLE 18

This example describes the preparation of4-bromo-3-(4-chloro-2-fluoro-5-methoxyphenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole(Compound No. 313).

A. A solution of 3.16 g (7.9 mmole)4-bromo-3-(2-fluoro-5-methoxy-4-nitrophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazolein 59 mL acetic acid was heated to 80° C. under a nitrogen atmosphere.The heat and nitrogen were removed and 1.76 g (31.6 mmole) iron powderwas added in 3 portions over 5 min. The solution was stirred at 80° C.for an additional 30 min. The solution was cooled and filtered throughCelite®. The filtrate was diluted with 100 mL water and extracted threetimes with diethyl ether. The ether extracts were washed with brine,dried over anhydrous MgSO₄, and concentrated in vacuo. The residue waspurified chromatographically using 40% ethyl acetate in hexane as theeluent to give 2.4 g (83%) of4-(4-bromo-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-5-fluoro-2-methoxy-benzeneamineas a white solid, mp 85°-86° C.

Anal. Calc. for C₁₂ H₁₀ Br₁ F₄ N₃ O₁ : C,39.15; H,2.74; N,11.41. Found:C,39.13; H,2.74; N,11.40.

B. All equipment was flame dried under nitrogen. A solution of 6.6 g(0.0179 mole) of the product of step A in 100 mL acetonitrile was cooledto 5° C. 1.8 g (0.018 mole) CuCl and 3.7 g (0.027 mole) CuCl₂ were addedat 5° C. A solution of 4.8 mL (0.036 mole) 90% t-butyl nitrite in 15 mLacetonitrile was added over 15 minutes. The reaction mixture was stirredat 5° C. for 15 minutes and then allowed to warm to 28° C. After 2 hoursat 28° C. the reaction mixture was stripped in vacuo. The reactionresidue was taken up in diethyl ether and washed three times with a 10%HCl solution, two times with brine and dried over anhydrous MgSO₄, andconcentrated in vacuo. The residue was purified chromatographicallyusing 20% ethyl acetate in hexane as the eluent to give 6.3 g (91%) of4-bromo-3-(4-chloro-2-fluoro-5-methoxyphenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazoleas a white solid, mp 85°-86° C.

Anal. Calc. for C₁₂ H₈ Br₁ Cl₁ F₄ N₂ O₁ : C,37.19; H,2.08; N,7.23.Found: C,37.23; H,2.08; N,7.24.

EXAMPLE 19

This example describes the preparation of4-chloro-3-(5-chloro-2,4-difluorophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole(Compound No. 354).

A. A solution of 3.4 g (0.01 mole)4-chloro-3-(2,4-difluoro-5-nitrophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazolein 50 mL acetic acid was heated to 80° C. under a nitrogen atmosphere.The heat and nitrogen were removed and 1.7 g (0.03 mole) iron powder wasadded in 3 portions over 5 min. The solution was stirred at 80° C. foran additional 30 min. The solution was cooled and filtered throughCelite®. The filtrate was diluted with 100 mL water and extracted threetimes with ethyl acetate. The ethyl acetate extracts were washed with asaturated NaHCO₃ solution, dried over anhydrous MgSO₄, and concentratedin vacuo. The residue was purified chromatographically using 35% ethylacetate in hexane as the eluent to give 2.46 g (79%) of5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-2,4-difluorobenzenamineas a white solid, mp 82° C.

Anal. Calc. for C₁₁ H₇ Cl₁ F₅ N₃ : C,42.40; H,2.26; N,13.48. Found:C,42.40; H,2.26; N,13.49.

B. All equipment was flame dried under nitrogen. A solution of 2.0 g(6.4 mmole) of the product of step A in 50 mL acetonitrile at 25° C. wastreated with 0.63 g (6.4 mmole) CuCl and 1.2 g (9.4 mmole) of CuCl₂. Asolution of 1.74 mL (5.0 mmole) 90% t-butyl nitrite was added over 5minutes. After 4 hours at 28° C. the reaction mixture was stripped invacuo. The reaction residue was taken up in ethyl acetate and washedthree times with a 10% HCl solution, two times with brine and dried overanhydrous MgSO₄, and concentrated in vacuo. The residue was purifiedchromatographically using 10% ethyl acetate in hexane as the eluent togive 1.63 g (78%) of4-chloro-3-(5-chloro-2,4-difluorophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazoleas a white solid, mp 50°-51° C.

Anal. Calc. for C₁₁ H₅ Cl₂ F₅ N₂ : C,39.91; H,1.52; N,8.46. Found:C,39.89; H,1.52; N,8.39.

Examples 20 and 21 describe working embodiments of Process VI.

EXAMPLE 20

This example describes the preparation of4-chloro-3-(4-chloro-2-fluoro-5-hydroxyphenyl)-1-methyl-5-(hydroxyphenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole (Compound No.325).

1.39 g of4-chloro-3-(4-chloro-2-fluoro-5-methoxyphenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazolewas dissolved in 80 ml of anhydrous methylene chloride and then cooledwith a dry ice/acetone bath and 0.14 ml of boron tribromide added. Afterallowing to warm to room temperature, the mixture was treated with anadditional 0.28 ml of boron tribromide. Added was an additional 1.0 mlof boron tribromide and stirred at room temperature for 6 hours. Afterstirring, 30-50 ml of ice cooled water was added and the mixture stirredfor 10 minutes. The organic phase was extracted with water, dried withanhydrous magnesium sulfate, filtered and concentrated to give 1.28 g of4-chloro-3-(4-chloro-2-fluoro-5-hydroxyphenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole,m.p. 123.0°-126.0° C.

Anal. Calc. for C₁₁ H₆ N₂ O₁ Cl₂ F₄ : C,40.15; H,1.84; N,8.51. Found:C,40.08; H,1.87; N,8.48.

EXAMPLE 21

This example describes the preparation of4-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-5-fluoro-2-nitrophenol(Compound No. 429).

A solution of 1.4 g (4 mmole)4-chloro-3-(2-fluoro-4-methoxy-5-nitrophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazolein 20 mL methylene chloride was chilled to 0° C. Next 5.0 mL of a 1Mmethylene chloride solution of BBr₃ (4.9 mmole) was added slowly over 10minutes. The solution was allowed to stir overnight at room temperature.The solution was washed two times with water, dried over anhydrousMgSO₄, and concentrated in vacuo. The residue was recrystallized fromhexane to give 0.7 g (54%) of4-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-5-fluoro-2-nitrophenolas a beige solid, mp 89°-90° C.

Anal. Calc. for C₁₁ H₆ Cl₁ F₄ N₃ O₃ : C,38.90; H,1.78; N,12.37. Found:C,38.93; H,1.78; N,12.16.

Examples 22 through 24 describe specific working embodiments of ProcessVII.

EXAMPLE 22

This example describes the preparation of4-chloro-3-(4-chloro-2-fluoro-5-progargyloxyphenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole(Compound No. 261).

1.01 g of4-chloro-3-(4-chloro-2-fluoro-5-hydroxyphenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole,0.44 g of anhydrous potassium carbonate and 0.5 mL of propargyl bromide(80% by wt. in toluene) were dissolved in 20-30 mL of anhydrous DMF. Themixture was heated at 65° C. for 90 minutes. After cooling, the mixturewas diluted with water and then extracted three times with ether. Thecombined ether extracts were extracted twice with water, dried withanhydrous magnesium sulfate, filtered, concentrated and chromatographedto give 1.05 g of4-chloro-3-(4-chloro-2-fluoro-5-progargyloxyphenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole,mp. 89.5°-91.0° C.

Anal. Calc. for C₁₄ H₈ N₂ O₁ Cl₂ F₄ : C,45.80%; H,2.20%; N,7.63%. Found:C,45.93%; H,2.21%; N,7.61%.

EXAMPLE 23

This example describes the preparation of(4-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-5-fluoro-2-nitrophenoxy)aceticacid, ethyl ester (Compound No. 386).

At 25° C., 6.11 g (0.018 mole)4-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-5-fluoro-2-nitrophenol,2.5 g (0,019 mole) K₂ CO₃, and 2.0 mL (0.019 mole) ethyl bromoacetatewere slurried in 100 mL acetone. The reaction mixture was stirred at 40°C. for 4 hours. The mixture was cooled, diluted with 100 mL cold water,and extracted four times with ethyl acetate. The ethyl acetate extractswere washed with brine, dried over anhydrous MgSO₄, and stripped invacuo. The residue was recrystallized from methylcyclohexane to give 7.5g (99%) of(4-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-5-fluoro-2-nitrophenoxy)aceticacid, ethyl ester as a light yellow solid, mp 95°-96° C.

Anal. Calc. for C₁₅ H₁₂ Cl₁ F₄ N₃ O₅ : C,42.32; H,2.84; N,9.87. Found:C,42.30; H,2.83; N,9.85.

EXAMPLE 24

This example describes the preparation of(2-chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorophenoxy)aceticacid, ethyl ester (Compound No. 290).

At 25° C., 13.16 g (0.04 mole)4-chloro-3-(4-chloro-2-fluoro-5-hydroxyphenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole,6.1 g (0.044 mole) K₂ CO₃, and 4.8 mL (0.044 mole) ethyl bromoacetatewere slurried in 25 mL acetone. The reaction mixture was stirred at 25°C. for 16 hours. The reaction solution was poured into 150 mL ice water,filtered, washed with water and air dried. The residue wasrecrystallized from hexane to give 16.6 g (100%) of(2-chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorophenoxy)aceticacid, ethyl ester as a white solid, mp 130°-131° C.

Anal. Calc. for C₁₅ H₁₂ Cl₁ F₄ N₂ O₃ : C,43.40; H,2.91; N,6.75. Found:C,43.54; H,2.91; N,6.77.

Examples 25 and 26 describe specific working embodiments of ProcessVIII.

EXAMPLE 25

This example describes the preparation of2-(2-chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorophenoxy)-N-methyl-propanamide(Compound No. 237).

A. To a slurry of 1.4 g (3.3 mmole)2-(2-chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorophenoxy)-propanoicacid, ethyl ester in 50 mL water and 30 mL 1,4-dioxane was added 1.3 mL(3.3 mmole) of a 10% NaOH solution. After 30 minutes, the solution wascooled and the pH adjusted to 3 with concentrated HCl. The reactionmixture was extracted with diethyl ether. The ether solution was washedwith water, dried over anhydrous MgSO₄, and concentrated in vacuo. Theresidue was recrystallized from methylcyclohexane to give 1.3 g (100%)of2-(2-chloro-5-(4-chloro-1-methyl-5-(tri-fluoromethyl)-1H-pyrazol-3-yl)-4-fluorophenoxy)propanoicacid as a white solid, mp 150°-151° C.

Anal. Calc. for C₁₄ H₁₀ Cl₂ F₄ N₂ O₃ : C,41.92; H,2.51; N,6.98. Found:C,41.96; H,2.48; N,7.00.

B. To a solution of 0.8 g (2.0 mmole) of the product of step A in 100 mLmethylene chloride was added 0.5 mL (6.0 mmole) oxalyl chloride over 5minutes, causing the evolution of gas. When this evolution ceased, onedrop of DMF was added and the solution stirred until the gas evolutionceased. The solution was stripped to dryness in vacuo. The residue wasdissolved in 10 mL THF and added to a solution of 5 mL 40% aqueousmethyl amine and 10 mL THF at 0° C. over 5 minutes. The reaction mixturewas allowed to stir for 30 minutes at room temperature. The solution wasdiluted with 100 mL cold water and extracted with ethyl acetate. Theethyl acetate was washed with brine, dried over anhydrous MgSO₄ andconcentrated in vacuo. The solid was recrystallized frommethylcyclohexane to give 0.83 g (99%) of2-(2-chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorophenoxy)-N-methylpropanamide as a white solid,mp 134.5°-135.5° C.

Anal. Calc. for C₁₅ H₁₃ Cl₂ F₄ N₃ O₂ : C,43.50; H,3.16; N,10.16. Found:C,43.70; H,3.16; N,10.20.

EXAMPLE 26

This example describes the preparation of2-(2-chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorophenoxy)propanoicacid, 3-methylbutyl ester (Compound No. 288).

To a solution of 1.9 g (5.0 mmole) of2-(2-chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorophenoxy)-propanoicacid in 50 mL methylene chloride was added 1.3 mL (15.0 mmole) oxalylchloride over 5 minutes, causing the evolution of gas. When thisevolution ceased, one drop of DMF was added and the solution stirreduntil the gas evolution ceased. The solution was stripped to dryness invacuo. The acid chloride was dissolved in 40 mL of 3-methyl-1-butanoland heated to reflux for one hour. The reaction mixture was cooled,diluted with 100 mL cold water and extracted with ethyl acetate. Theethyl acetate was washed with brine, dried over anhydrous MgSO₄ andconcentrated in vacuo. The residue was purified chromatographicallyusing 25% ethyl acetate in hexane as the eluent to give 2.17 g (95%) of2-(2-chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorophenoxy)-propanoicacid, 3-methylbutyl ester as a white solid; mp 128° C.

Anal. Calc. for C₁₈ H₁₈ Cl₂ F₄ N₂ O₃ : C,47.28; H,3.97; N,6.13. Found:C,47.32; H,3.95; N,6.17.

EXAMPLE 27

This example describes the preparation of 2H-1,4-benzoxazin-3(4H)-one,6-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-7-fluoro-4-(2-propynyl)-2H-1,4-benzoxazin-3(4H)-one (Compound No. 446) and is a specificembodiment of Process IX.

A. A solution of 4.5 g (0.0106 mole)(4-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-5-fluoro-2-nitrophenoxy)-aceticacid, ethyl ester in 75 mL acetic acid was heated to 80° C. under anitrogen atmosphere. The heat and nitrogen were removed and 1.8 g (0.033mole) iron powder was added in 3 portions over 5 min. The solution wasstirred at 80° C. for an additional 3 hours. The solution was cooled andfiltered through Celite®. The filtrate was diluted with 100 mL water andextracted three times with ethyl acetate. The ethyl acetate extractswere washed with a saturated NaHCO₃ solution, dried over anhydrousMgSO₄, and concentrated in vacuo. The residue was recrystallized frommethylcyclohexane/ethyl acetate to give 2.95 g (80%) of6-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-7-fluoro-2H-1,4-benzoxazin-3(4H)-oneas a white solid, mp 207° C.

Anal. Calc. for C₁₃ H₈ Cl₁ F₄ N₃ O₂ : C,44.65; H,2.31; N,12.02. Found:C,44.66; H,2.31; N,11.97.

B. At 25° C., 3.0 g (8.6 mmole) of the product of step A, 1.22 g (6.0mmole) K₂ CO₃ and 0.79 mL (8.8 mmole) 80% propargyl bromide wereslurried in 50 mL acetone. The reaction was stirred at 40° C. for 6hours. The reaction was cooled, diluted with 100 mL cold water, andextracted four times with ethyl acetate. The ethyl acetate extracts werewashed with brine, dried over anhydrous MgSO₄, and stripped in vacuo.The residue was recrystallized from methylcyclohexane to give 2.97 g(89%) of 2H-1,4-benzoxazin-3(4H)-one,6-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-7-fluoro-4-(2-propynyl)-2H-1,4-benzoxazin-3(4H)-oneas a beige solid, mp 142°-143° C.

Anal. Calc. for C₁₆ H₁₀ Cl₁ F₄ N₃ O₂ : C,49.57; H,2.60; N,10.84. Found:C,49.58; H,2.62; N,10.85.

EXAMPLE 28

This example describes the preparation of7-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-6-fluoro-4-(2-propynyl)-2H-1,4-benzoxazin-3(4H)-one(Compound No. 479) and is a specific embodiment of Process X.

A. A solution of 2.3 g (5.4 mmole)(5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluoro-2-nitrophenoxy)aceticacid, ethyl ester in 50 mL acetic acid was heated to 80° C. under anitrogen atmosphere. The heat and nitrogen were removed and 0.9 g (16.2mmole) iron powder was added in 3 portions over 5 minutes. The solutionwas stirred at 80° C. for an additional 50 minutes. The solution wascooled and filtered through Celite®. The filtrate was diluted with 100mL water and extracted three times with ethyl acetate. The ethyl acetateextracts were washed with a saturated NaHCO₃ solution, dried overanhydrous MgSO₄ and concentrated in vacuo. The residue wasrecrystallized from methylcyclohexane/ethyl acetate to give 0.96 g (50%)of7-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-6-fluoro-2H-1,4-benzoxazin-3(4H)-oneas a white solid, mp 242° C.

Anal. Calc. for C₁₃ H₈ Cl₁ F₄ N₃ O₂ : C,44.65; H,2.31; N,12.02. Found:C,44.61; H,2.27; N,11.99.

B. At 25° C., 2.7 g (7.7 mmole) the product of step A, 1.1 g (8.0 mmole)K₂ CO₃ and 0.9 mL (8.0 mmole) 80% propargyl bromide were slurried in 25mL DMSO. The mixture was stirred at 45° C. for 16 hours. The mixture wascooled, diluted with 100 mL cold water and extracted four times withethyl acetate. The ethyl acetate extracts were washed with brine, driedover anhydrous MgSO₄ and stripped in vacuo. The residue was purifiedchromatographically using methylene chloride as the eluent to give 2.7 g(90%) of7-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-6-fluoro-4-(2-propynyl)-2H-1,4-benzoxazin-3(4H)-oneas a white solid, mp 184° C.

Anal. Calc. for C₁₆ H₁₀ Cl₁ F₄ N₃ O₂ : C,49.57; H,2.60; N,10.84. Found:C,49.48; H,2.56; N,10.95.

EXAMPLE 29

This example describes the preparation of cis- andtrans-4-chloro-3-(3-(chloromethylene)-5-fluoro-2,3-dihydro-6-benzofuranyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole(Compound Nos. 481 and 482) and is a specific embodiment of Process XI.

All equipment was flame dried under nitrogen. A solution of 2.0 g (5.75mmole)4-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-5-fluoro-2-(2-propynloxy)-benzeneaminein 100 mL acetonitrile at 25° C. was treated with 0.6 g (5.75 mmole)CuCl and 0.8 g (5.75 mmole) CuCl₂. A solution of 1.1 mL (8.6 mmole) 90%t-butyl nitrite was added over 5 minutes. After 6 hours at 28° C. thereaction mixture was stripped in vacuo. The reaction residue was takenup in ethyl acetate and washed three times with a 10% HCl solution, twotimes with brine and dried over anhydrous MgSO₄ and concentrated invacuo. The residue was purified chromatographically using 20% ethylacetate in hexane as the eluent to give 0.73 g (35%) ofcis-4-chloro-3-(3-(chloromethylene)-5-fluoro-2,3-dihydro-6-benzofuranyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazoleas a white solid, mp 140.5°-142.5° C.

Anal. Calc. for C₁₄ H₈ Cl₂ F₄ N₂ O₁ : C,45.80; H,2.20; N,7.63; C₁,19.31.Found: C,45.64; H,2.22; N,7.60; C₁,19.29.

The chromatography described above gave a second fraction following themain component. This fraction was collected, stripped and the residuecrystallized from hexanes to give 0.68 g (32% yield) oftrans-4-chloro-3-(3-(chloromethylene)-5-fluoro-2,3-dihydro-6-benzo-furanyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazoleas a beige solid, mp 132°-135° C.

Anal. Calc. for C₁₄ H₈ Cl₂ F₄ N₂ O₁ : C,45.80; H,2.20; N,7.63; Cl,19.31.Found: C,45.71; H,2.23; N,7.63; Cl,19.28.

Examples 30 through 37 describe working embodiments of Process XII.

EXAMPLE 30

This example describes the preparation of3-[5-(bromomethyl)-4-chloro-2-fluorophenyl]-4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazole(Compound No. 108).

A slurry of3-[5-methyl-4-chloro-2-fluorophenyl]-4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazole(25 g, 76.4 mmole) and N-bromosuccinimide (13.6 g, 76.4 mmole) in 100 mlof carbon tetrachloride in a 500 ml round bottomed flask equipped with amagnetic stirrer was treated with a catalytic amount of benzoylperoxide. The temperature was raised to reflux for one hour. Thereaction mixture was cooled to room temperature, filtered andconcentrated to give 31.5 g of white solid. The material wasrecrystallized twice from hexanes to afford 15.3 g (49%) of3-[5-(bromomethyl)-4-chloro-2fluorophenyl]-4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazoleas a white solid; mp 112°-114° C.

Anal. Calc. for C₁₂ H₇ N₂ F₄ Cl₂ Br₁ : C,35.50; H,1.74; N,6.90. Found:C,35.57; H,1.76; N,6.88.

EXAMPLE 31

This example describes the preparation of(((2-chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorophenyl)methyl)thio)acetic acid, ethyl ester (Compound No.123).

A mixture of 1.62 g (4.0 mmole)3-[5-(bromomethyl)-4-chloro-2-fluorophenyl]-4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazole,0.44 mL ethyl mercaptoacetate and 0.55 g K₂ CO₃ was slurried in 25 mL ofacetone. The reaction mixture was allowed to stir at room temperatureovernight. After dilution with 100 mL of cold water, the mixture wasextracted with ethyl acetate, the organic extracts washed with water,dried with MgSO₄ and concentrated in vacuo. The residue was purified bychromatography to afford 1.7 g (96%) of(((2-chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorophenyl)methyl)thio)aceticacid, ethyl ester as a white solid; mp 63° C.

Anal. Calc. for C₁₆ H₁₄ Cl₂ F₄ N₂ O₂ S₁ : C,43.16; H,3.17; N,6.29.Found: C,43.16; H,3.16; N,6.27.

EXAMPLE 32

This example describes the preparation of2-chloro-5-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzenemethanol(Compound No. 122).

To a solution of 7.1 g (0.0175 mole)3-[5-(bromomethyl)-4-chloro-2-fluorophenyl]-4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazolein 20 mL DMF was added 1.5 g (0.018 mole) sodium acetate. The mixturewas stirred for 12 hours at 25° C. The mixture was poured into 100 mLcold water and the solid filtered and dried. The product wasrecrystallized from ethanol/-water to give 6.0 g (90%) of2-chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorobenzenemethanol,acetate (ester), mp 90° C. The acetate was dissolved in 10 mL1,4-dioxane and 10 mL water and 6.3 mL (0.0158 mole) 10% NaOH solutionwas added. After 30 minutes the solution was neutralized withconcentrated HCl, filtered and the solid dried. The solid wasrecrystallized from ethanol/water to give 5.4 g (99%) of2-chloro-5-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzenemethanolas a white solid; mp 103° C.

Anal. Calc. for C₁₂ H₈ N₂ O₁ F₄ Cl₂ : C,42.01; H,2.35; N,8.16. Found:C,41.88; H,2.34; N,8.09.

EXAMPLE 33

This example describes the preparation of((2-chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorophenyl)methoxy)aceticacid, 1-methylethylester (Compound No. 119).

At 25° C., 1.7 g (5.0 mmole)2-chloro-5-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzenemethanol,0.8 g (5.5 mmole) K₂ CO₃ and 0.7 mL (5.5 mmole) isopropyl bromoacetatewere slurried in 15 mL DMSO. The mixture was stirred overnight at 45° C.The mixture was cooled, diluted with 100 mL cold water and extractedfour times with ethyl acetate. The ethyl acetate extracts were washedwith brine, dried over anhydrous MgSO₄ and stripped in vacuo. Theresidue was purified chromatographically using 10% ethyl acetate inhexane as the eluent to give 0.9 g (41%) of((2-chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-Pyrazol-3-yl)-4-fluorophenyl)methoxy)aceticacid, 1-methylethyl ester as a white solid; mp 55° C.

Anal. Calc. for C₁₇ H₁₆ Cl₂ F₄ N₂ O₃ : C,46.07; H,3.64; N,6.32. Found:C,46.21; H,3.69; N,6.11.

EXAMPLE 34

This example describes the preparation of4-chloro-3-[4-chloro-5-(dibromomethyl)-2-fluorophenyl]-1-methyl-5-(trifluoromethyl)-1H-Pyrazole(Compound No. 132).

In a 250 ml round bottomed flask equipped with a magnetic stirrer, aslurry of3-[5-methyl-4-chloro-2fluorophenyl]-4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazole(8.18 g, 25 mmole) and N-bromosuccinimide (8.9 g, 50.0 mmole) wasprepared in 50 ml of carbon tetrachloride. A catalytic amount of benzoylperoxide was added and the temperature was raised to reflux and held for3.5 hours. The reaction mixture was cooled to room temperature, filteredand concentrated. The residue was purified by chroma-tography to afford10.36 g (85%) of4-chloro-3-[4-chloro-5-(dibromomethyl)-2-fluorophenyl]-1-methyl-5-(tri-fluoromethyl)-1H-pyrazoleas a white solid; mp 89°-92 ° C.

Anal. Calc. for C₁₂ H₆ N₂ F₄ Cl₂ Br₂ ; C,29.72; H,1.25; N,5.78. Found:C,29.72; H,1.25; N,5.78.

EXAMPLE 35

This example describes the preparation of2-chloro-5-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzaldehyde(Compound No. 133).

In a 100ml round bottomed flask equipped with a magnetic stirrer,4-chloro-3-[4-chloro-5-(dibromomethyl)-2-fluorophenyl]-1-methyl-5-(trifluoromethyl)-1-H-pyrazole(5.0 g, 10.3 mmole) was stirred for 30 minutes in 20 ml of sulfuricacid. The resulting clear yellow solution was allowed to stand at roomtemperature for 10 days, stirred briefly to remove color, and pouredonto 200 ml of ice/water. The aqueous mixture was extracted with etherand the organic layer was dried with MgSO₄, filtered and concentrated togive 3.15 g of white solid which was recrystallized from cold hexanes toafford 2.5 g (71%) of2-chloro-5-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzaldehydeas a white solid; mp 70°-72° C.

Anal. Calc. for C₁₂ H₆ N₂ O₁ F₄ Cl₂ : C,42.26; H,1.77; N,8.21. Found:C,42.22; H,1.78; N,8.24.

EXAMPLE 36

This example describes the preparation of2-chloro-5-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzoicacid (Compound No. 149).

To a solution of2-chloro-5-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzaldehyde(4.5 g, 13.2 mmole) in 40 ml of acetone was added 13 ml (26 mmole) ofJones' reagent. The solution was stirred at ambient temperature for 2hours and poured into 400 ml of water. The resulting solid was filteredand air dried overnight to afford 4.5 g (96%) of2-chloro-5-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-Pyrazol-3-yl]-4-fluoro-benzoicacid as a white solid. An analytical sample was recrystallized fromether/hexanes; mp 179°-181° C.

Anal. Calc. for C₁₃ H₆ N₂ O₂ F₄ Cl₂ : C,40.36; H,1.69; N,7.84. Found:C,40.49; H,1.74; N,7.77.

EXAMPLE 37

This example describes the preparation of2-chloro-5-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzoicacid, 1-methylethyl ester (Compound No. 135).

To a solution of 4.3 g (0.012 mole)2-chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-Pyrazol-3-yl)-4-fluorobenzoicacid in 50 mL methylene chloride was added 3.1 mL (0.036 mole) oxalylchloride causing the evolution of gas. When this evolution ceased, onedrop of DMF was added and the solution stirred until the gas evolutionceased. The solution was concentrated in vacuo and the resultant residuedissolved in 25 mL isopropanol and heated to 60° C. for 1 hour. Thesolution was cooled, poured into 200 mL cold water and the solidfiltered and dried. The product was recrystallized from ethanol/water toyield 1.69 g (70%) of2-chloro-5-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-Pyrazol-3-yl]-4-fluorobenzoicacid, 1-methylethyl ester as a white solid; mp 69° C.

Anal. Calc. for C₁₅ H₁₂ Cl₂ F₄ N₂ O₂ : C,45.13; H,3.03; N,7.02. Found:C,45.14; H,3.04; N,7.03.

Examples 38 and 39 describe working embodiments of Process XIII.

EXAMPLE 38

This example describes the preparation of2-chloro-5-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzenesulfonylchloride (Compound No. 346).

A solution of4-chloro-3-(4-chloro-2-fluorophenyl)-1-methyl-5-(trifluoromethyl)-1H-Pyrazolein 20 mL of chlorosulfonic acid was heated in a 120° C. oil bath forfour hours and allowed to cool to room temperature. Methylene chloridewas added and the solution added dropwise to a stirring mixture of iceand water (caution, extremely reactive). The layers were separated andthe aqueous layer was washed with methylene chloride. The combinedorganic layers were dried with MgSO₄, filtered and concentrated and theresultant solid residue washed with a very small amount of ether andrecrystallized from hexanes to afford 1.65 g (63%) of2-chloro-5-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzenesulfonylchloride as a white solid; mp 116°-117° C.

Anal. Calc. for C₁₁ H₅ N₂ O₂ S₁ F₄ Cl₃ : C,32.10; H,1.22; N,6.81;C₁,25.84. Found: C,32.15; H,l.17; N,6.76; C₁,25.77.

Example 39

This example describes the preparation of2-chloro-5-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzenethiol(Compound No. 343).

To a solution of 12.8 g (0.031 mole) 2-chloro-5[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzenesulfonylchloride in 100 mL acetic acid was added 40.7 g (0.62 mole) zinc powder.The slurry was stirred at 80° C. for 4 hours, allowed to cool andfiltered through Celite®. The filtrate was poured into 1.0 L water, thesolid filtered and dried. The solid was recrystallized fromethanol/water to give 10.2 g (95%) of2-chloro-5-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzenethiolas a yellow solid; mp 56°-58° C.

Anal. Calc. for C₁₁ H₆ N₂ S₁ F₄ Cl₂ : C,38.28; H,1.75; N,8.12. Found:C,38.29; H,2.02; N,8.12.

EXAMPLE 40

This example describes the preparation of4-chloro-3-(4-chloro-5-(1,3-dioxolan-2-yl)-2-fluorophenyl)-1-methyl-5-(trifluoromethyl)-1H-Pyrazole(Compound No. 100) and is a specific embodiment of Process XIV.

In an apparatus equipped with a Dean-Stark trap for azeotropic removalof water, 2.4 g (7.0 mmoles)2-chloro-5-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzaldehyde,0.4 mL (7.7 mmoles) ethylene glycol and a catalytic amount ofp-toluenesulfonic acid in 50 mL toluene was heated to reflux for 24hours. The resultant mixture was concentrated and the residue purifiedby chromatography to give 1.65 g (61%) of4-chloro-3-(4-chloro-5-(1,3-dioxolan-2-yl)-2-fluorophenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazoleas a clear colorless oil; n_(D) ²⁵ 51.5348.

Anal. Calc. for C₁₄ H₁₀ Cl₂ F₄ N₂ O₂ : C,43.66; H,262; N,7.27. Found:C,43.67; H,2.59; N,7.24.

EXAMPLE 41

This example describes the preparation of3-(2-chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorophenyl)propenoicacid, methyl ester (Compound No. 128) and is a specific embodiment ofProcess XV.

To a solution of 2.3 g (6.8 mmole)2-chloro-5-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzaldehydein 25 mL methanol was added 2.27 g (6.8 mmole)methyl(triphenylphosphoranylidene)acetate, keeping the temperature below35° C. The reaction mixture was allowed to stir for 15 minutes anddiluted with ethyl acetate, washed with brine, dried over anhydrousMgSO₄, and concentrated in vacuo. The residue was purifiedchromatographically using 20% ethyl acetate in hexane as the eluent togive 2.0 g (74%) of3-(2-chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorophenyl)propenoicacid, methyl ester as a white solid; mp 117° C.

Anal. Calc. for C₁₅ H₁₀ Cl₂ F₄ N₂ O₂ : C,45.36; H,2.54; N,7.05. Found:C,45.41; H,2.59; N,7.03.

EXAMPLE 42

This example describes the preparation of((((2-chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorophenyl)methylene) amino)oxy)acetic acid(Compound No. 130) and is a specific embodiment of Process XVI.

A mixture of 3.4 g (0.01 mole)2-chloro-5-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorobenzaldehyde,2.73 g (0.0125 mole) carboxymethoxylamine hemihydrochloride and 1.03 g(0.0125 mole) sodium acetate in 50 mL ethanol was heated to reflux for 2hours. The reaction mixture was allowed to cool, treated with 150 mL ofwater and the resultant precipitate collected and dried. The product wasrecrystallized from methylcyclohexane with a minimum amount of ethylacetate to yield 3.35 g (81%) of((((2-chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorophenyl)methylene)amino)oxy)aceticacid as a white solid; mp 170° C.

Anal. Calc. for C₁₄ H₁₉ Cl₂ F₄ N₃ O₃ : C,40.60; H,2.19; N,10.15. Found:C,40.54; H,2.28; N, 10.17.

Tables 4-6 show examples of compounds prepared according to ProcessesII-XVI. In Table 4 are listed examples of 1-methyl-5-arylpyrazoleCompounds. In Table 5 are examples of 1-methyl-3-arylpyrazoles. Table 6lists a variety of compounds, most of which include compounds wherein R₆and R₇ are cyclized to form fused-ring heterocyclic structures.

                                      TABLE 4                                     __________________________________________________________________________    PHYSICAL DATA FOR 1-METHYL-5-ARYLPYRAZXOLES                                    ##STR26##                                                                    Compound                    physical data                                     No.   R.sub.2                                                                           R.sub.3                                                                         R.sub.5                                                                         R.sub.6                                                                           R.sub.7   (mp, bp, nD)                                      __________________________________________________________________________    62    CF.sub.2 H                                                                        Cl                                                                              F H   F         nD, 1.5162 (25° C.)                        63    CF.sub.3                                                                          Cl                                                                              F Cl  CH.sub.3  71.0-72.0° C.                              64    CF.sub.2 H                                                                        Cl                                                                              F Cl  CH.sub.3  91.0° C.                                   65    CF.sub.3                                                                          Cl                                                                              H NO.sub.2                                                                          H         122.5-123.5° C.                            66    CF.sub.3                                                                          Cl                                                                              H Cl  H         68.9-69.6° C.                              67    CF.sub.2 Cl                                                                       Cl                                                                              H Cl  H         65.1-66.0° C.                              68    CF.sub.3                                                                          Br                                                                              F H   F         53.0° C.                                   69    CF.sub.3                                                                          Cl                                                                              F H   F         69.0° C.                                   70    CF.sub.3                                                                          Cl                                                                              F NO.sub.2                                                                          F         88.0° C.                                   71    CF.sub.3                                                                          Cl                                                                              F OCH.sub.3                                                                         F         nD 1.5062 (25° C.)                         72    CF.sub.3                                                                          Cl                                                                              F NO.sub.2                                                                          OCH.sub.3 123.0-124.0° C.                            73    CF.sub.3                                                                          Cl                                                                              F NH2 OCH.sub.3 120.0-120.5° C.                            74    CF.sub.3                                                                          Cl                                                                              F Cl  OCH.sub.3 100.0° C.                                  75    CF.sub.3                                                                          Cl                                                                              F F   H         43.0-44.0° C.                              76    CF.sub.3                                                                          Cl                                                                              F Cl  OCH.sub.2 CCH                                                                           116.5-117.0° C.                            77    CF.sub.3                                                                          Cl                                                                              F F   NO.sub.2  57.0-58.5° C.                              78    CF.sub.3                                                                          Cl                                                                              F OCH.sub.3                                                                         NO.sub.2  108.0° C.                                  79    CF.sub.3                                                                          Cl                                                                              F Cl  H         73.0-74.0° C.                              80    CF.sub.3                                                                          Cl                                                                              Cl                                                                              Cl  F         71.5-72.5° C.                              __________________________________________________________________________

                                      TABLE 5                                     __________________________________________________________________________    PHYSICAL DATA FOR 1-METHYL-3-ARYLPYRAZOLES                                     ##STR27##                                                                                                                   physical data                  Compound No.                                                                          R.sub.2                                                                           R.sub.3                                                                         R.sub.5                                                                         R.sub.6   R.sub.7              (mp, bp,                       __________________________________________________________________________                                                   nD)                             81     CF.sub.3                                                                          Cl                                                                              H NO.sub.2  H                    93.0-95.0° C.            82     CF.sub.3                                                                          Cl                                                                              H Cl        H                    68.2-69.2° C.            83     CF.sub.2 Cl                                                                       Cl                                                                              H Cl        H                    37.0-38.4° C.            84     CF.sub.3                                                                          Cl                                                                              Cl                                                                              Cl        F                    64.0° C.                 85     CF.sub.3                                                                          Cl                                                                              Cl                                                                              Cl        H                    78.5-79.5° C.            86     CF.sub.3                                                                          Cl                                                                              Cl                                                                              Cl        NO.sub.2             118.0-120.0° C.          87     CF.sub.3                                                                          Cl                                                                              Cl                                                                              Cl        N(SO.sub.2 CH.sub.3).sub.2                                                                         137.0° C.                88     CF.sub.3                                                                          Cl                                                                              Cl                                                                              Cl        NHCOCF.sub.3         125.0° C.                89     CF.sub.3                                                                          Cl                                                                              Cl                                                                              Cl        SO.sub.2 Cl          127.0-128.0° C.          90     CF.sub.3                                                                          Cl                                                                              Cl                                                                              Cl        N(SO.sub.2 CH.sub.2 CH.sub.3).sub.2                                                                185.0° C.                91     CF.sub.3                                                                          Cl                                                                              Cl                                                                              Cl        NHSO.sub.2 CH.sub.3  160.0° C.                92     CF.sub.3                                                                          Cl                                                                              Cl                                                                              Cl        NHSO.sub.2 CH.sub.2 CH.sub.3                                                                       125.0° C.                93     CF.sub.3                                                                          Cl                                                                              Cl                                                                              Cl        SH                   100.0° C.                94     CF.sub.3                                                                          Cl                                                                              F Br        OCH.sub.3            76.0-77.0° C.            95     CF.sub.3                                                                          Cl                                                                              F Br        OH                   83.0-84.0° C.            96     CF.sub.3                                                                          Cl                                                                              F Br        OCH.sub.2 CCH        112.0-113.5° C.          97     CF.sub.3                                                                          Cl                                                                              F Br        OCH(CH.sub.3)CO.sub.2 Et                                                                           nD. 1.5217 (25°                                                        C.)                             98     CF.sub.3                                                                          Cl                                                                              F Cl        2-(4,5-DIHYDROOXAZOLYL)                                                                            110.0° C.                99     CF.sub.3                                                                          Cl                                                                              F Cl        4-MORPHOLINYL        98.0-99.0° C.           100     CF.sub.3                                                                          Cl                                                                              F Cl        2-(1,3-DIOXOLANYL)   nD 1.5348 (25° C.)      101     CF.sub.3                                                                          Cl                                                                              F Cl        2-(1,3-DITHIOLANYL)  clear colorless oil            102     CF.sub.3                                                                          Cl                                                                              F Cl        2-(1,3-OXATHIOLANYL) nD 1.5614 (25° C.)      103     CF.sub.3                                                                          Cl                                                                              F Cl        C(CH.sub. 3).sub.2 CN                                                                              nD, 1.5274 (25°                                                        C.)                            104     CF.sub.3                                                                          Cl                                                                              F Cl        C(CH.sub.3)NOCH.sub.2 CO.sub.2 Et                                                                  nD, 1.5203 (25°                                                        C.)                            105     CF.sub.3                                                                          Cl                                                                              F Cl        C(CH.sub.3)NOCH.sub.2 CONH.sub.2                                                                   96.0° C.                106     CF.sub.3                                                                          Cl                                                                              F Cl        CH(CH.sub.3)CN       nD, 1.5280 (25°                                                        C.)                            107     CF.sub.3                                                                          Cl                                                                              F Cl        CH(CH.sub.3)OH       85.0-87.0° C.           108     CF.sub.3                                                                          Cl                                                                              F Cl        CH.sub.2 Br          112.0-114.0° C.         109     CF.sub.3                                                                          Cl                                                                              F Cl        CH.sub.2 Cl          100.0-102.0° C.         110     CF.sub.3                                                                          Cl                                                                              F Cl        CH.sub.2 CO.sub.2 CH.sub.3                                                                         64.0-65.0° C.           111     CF.sub.3                                                                          Cl                                                                              F Cl        CH.sub.2 CO.sub.2 H  139.0-141.0° C.         112     CF.sub.3                                                                          Cl                                                                              F cl        CH.sub.2 CONH.sub.2  185.0-189.0° C.         113     CF.sub.3                                                                          Cl                                                                              F Cl        CH.sub.2 CONHCH.sub.2 CH.sub.2 Cl                                                                  187.0° C.               114     CF.sub.3                                                                          Cl                                                                              F Cl        CH.sub.2 CONHCH.sub.3                                                                              212.0° C.               115     CF.sub.3                                                                          Cl                                                                              F Cl        CH.sub. 2 CN         89.0-91.0° C.           116     CF.sub.3                                                                          Cl                                                                              F Cl        CH.sub.2 OCH.sub.2 CH.sub.2 F                                                                      57.0° C.                117     CF.sub.3                                                                          Cl                                                                              F Cl        CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3                                                              nD, 1.5155 (25°                                                        C.)                            118     CF.sub.3                                                                          Cl                                                                              F Cl        CH.sub.2 OCH.sub.2 CH.sub.3                                                                        34.0-37.0° C.           119     CF.sub.3                                                                          Cl                                                                              F Cl        CH.sub.2 OCH.sub.2 CO.sub.2 CH(CH.sub.3).sub.2                                                     55.0° C.                120     CF.sub.3                                                                          Cl                                                                              F Cl        CH.sub.2 OCH.sub.2 CCH                                                                             44.0° C.                121     CF.sub.3                                                                          Cl                                                                              F Cl        CH.sub.2 OCOCH.sub.3 90.0° C.                122     CF.sub.3                                                                          Cl                                                                              F Cl        CH.sub.2 OH          103.0-104.0° C.         123     CF.sub.3                                                                          Cl                                                                              F Cl        CH.sub.2 SCH.sub.2 CO.sub.2 Et                                                                     63.0° C.                124     CF.sub.3                                                                          Cl                                                                              F Cl        CH.sub.3             72.0-74.0° C.           125     CF.sub.3                                                                          Br                                                                              F Cl        CH.sub.3             93.0-95.0° C.           126     CF.sub.2 H                                                                        Cl                                                                              F Cl        CH.sub.3             115.0° C.               127     CF.sub.3                                                                          Cl                                                                              F Cl        CHC(CH.sub.3)CO.sub. 2 Et                                                                          54.0° C.                128     CF.sub.3                                                                          Cl                                                                              F Cl        ClCHCO.sub.2 CH.sub.3                                                                              117.0° C.               129     CF.sub.3                                                                          Cl                                                                              F Cl        CHNOCH.sub.2 CO.sub.2 Et                                                                           nD, 1.5330 (25°                                                        C.)                            130     CF.sub.3                                                                          Cl                                                                              F Cl        CHNOCH.sub.2 CO.sub.2 H                                                                            170.0° C.               131     CF.sub.3                                                                          Cl                                                                              F Cl        CHNOCH.sub.2 CONH.sub.2                                                                            169.0° C.               132     CF.sub.3                                                                          Cl                                                                              F Cl        CHBr.sub.2           89.0-92.0° C.           133     CF.sub.3                                                                          Cl                                                                              F Cl        CHO                  70.0-72.0° C.           134     CF.sub.3                                                                          Cl                                                                              F Cl        CO.sub.2 -cyclohexyl nD, 1.5287 (25°                                                        C.)                            135     CF.sub.3                                                                          Cl                                                                              F Cl        CO.sub.2 CH(CH.sub.3).sub.2                                                                        69.0° C.                136     CF.sub.3                                                                          Cl                                                                              F Cl        CO.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3                                                             nD, 1.5150 (25°                                                        C.)                            137     CF.sub.3                                                                          Cl                                                                              F Cl        CO.sub.2 CH(CH.sub.3)CO.sub.2 CH.sub.3                                                             nD, 1.5190 (25°                                                        C.)                            138     CF.sub.3                                                                          Cl                                                                              F Cl        CO.sub.2 CH(CH.sub.3)CO.sub.2 Et                                                                   nD, 1.5119 (25°                                                        C.)                            139     CF.sub.3                                                                          Cl                                                                              F Cl        CO.sub.2 CH.sub.2 CH(CH.sub.3).sub.2                                                               nD, 1.5158 (25°                                                        C.)                            140     CF.sub.3                                                                          Cl                                                                              F Cl        CO.sub.2 CH.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3                                                    nD, 1.5145 (25°                                                        C.)                            141     CF.sub.3                                                                          Cl                                                                              F Cl        CO.sub.2 CH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2                                                      nD, 1.5132 (25°                                                        C.)                            142     CF.sub.3                                                                          Cl                                                                              F Cl        CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                               64.0° C.                143     CF.sub.3                                                                          Cl                                                                              F Cl        CO.sub.2 CH.sub.2 CO.sub.2 Et                                                                      83.0° C.                144     CF.sub.3                                                                          Cl                                                                              F Cl        CO.sub.2 CH.sub.2 CCH                                                                              92.0° C.                145     CF.sub.3                                                                          Cl                                                                              F Cl        CO.sub.2 CH.sub.2 OCH.sub.3                                                                        77.0° C.                146     CF.sub.3                                                                          Cl                                                                              F Cl        CO.sub.2 CH.sub.3    78.0° C.                147     CF.sub.3                                                                          Cl                                                                              F Cl        CO.sub.2 CHFCO.sub.2 Et                                                                            nD, 1.5112 (25.°                                                       C.)                            148     CF.sub.3                                                                          Cl                                                                              F Cl        CO.sub.2 Et          88.0° C.                149     CF.sub.3                                                                          Cl                                                                              F Cl        CO.sub.2 H           179.0-180.0° C.         150     CF.sub.3                                                                          Cl                                                                              F Cl        CO.sub.2 n-butyl     clear oil                      151     CF.sub.3                                                                          Cl                                                                              F Cl        CO.sub.2 t-butyl     nD, 1.5130 (25°                                                        C.)                            152     CF.sub.3                                                                          Cl                                                                              F Cl        COCH.sub.3           134.0-135.0° C.         153     CF.sub. 3                                                                         Cl                                                                              F Cl        CON(CH.sub.3).sub.2  clear oil                      154     CF.sub.3                                                                          Cl                                                                              F Cl        CONHC(CH.sub.3).sub.2 CH.sub.2 OH                                                                  115.0° C.               155     CF.sub.3                                                                          Cl                                                                              F Cl        CONHCH.sub.2 CH.sub.2 Cl                                                                           129.0° C.               156     CF.sub.3                                                                          Cl                                                                              F Cl        CONHCH.sub.2 CH.sub.2 OH                                                                           143.0° C.               157     CF.sub.3                                                                          Cl                                                                              F Cl        CONHCH.sub.3         172.0° C.               158     CF.sub.3                                                                          Cl                                                                              F Cl        CONHN(CH.sub.3).sub.2                                                                              172.0° C.               159     CF.sub.3                                                                          Cl                                                                              F Cl        CONHOCH.sub.2 CO.sub.2 CH.sub.3                                                                    95.0° C.                160     CF.sub.3                                                                          Cl                                                                              F Cl        COSCH(CH.sub.3).sub.2                                                                              nD, 1.5475 (25°                                                        C.)                            161     CF.sub.3                                                                          Cl                                                                              F Cl        COSCH(CH.sub.3)CO.sub.2 Et                                                                         nD, 1.4723 (25°                                                        C.)                            162     CF.sub.3                                                                          Cl                                                                              F Cl        F                    45.5-46.5° C.           163     CF.sub.3                                                                          Cl                                                                              F Cl        H                    34.0-35.0° C.           164     CCl.sub.3                                                                         Cl                                                                              F Cl        H                    62.0-64.0° C.           165     CF.sub.2 H                                                                        Cl                                                                              F Cl        H                    61.0° C.                166     CF.sub.3                                                                          Cl                                                                              F Cl        N(CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.3                                                              nD, 1.5030 (25°                                                        C.)                            167     CF.sub.3                                                                          Cl                                                                              F Cl        N(COCF.sub.3)CH.sub.2 CHCH.sub.2                                                                   75.0° C.                168     CF.sub.3                                                                          Cl                                                                              F Cl        N(COCF.sub.3)CH.sub.2 CO.sub.2 Et                                                                  76.0-79.0° C.           169     CF.sub.3                                                                          Cl                                                                              F Cl        N(COCF.sub.3)CH.sub.2 CCH                                                                          nD, 1.5061 (25°                                                        C.)                            170     CF.sub.3                                                                          Cl                                                                              F Cl        N(COCF.sub.3)CH.sub.3                                                                              nD, 1.5004 (25°                                                        C.)                            171     CF.sub.3                                                                          Cl                                                                              F Cl        N(COCH.sub.3)CH(CH.sub.3).sub.2 COCH.sub.3                                                         140.0° C.               172     CF.sub.3                                                                          Cl                                                                              F Cl        N(SO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3).sub.2                                                       138.0° C.               173     CF.sub.3                                                                          Cl                                                                              F Cl        N(SO.sub.2 CH.sub.2 CH.sub.3).sub.2                                                                135.0,C                        174     CF.sub.3                                                                          Cl                                                                              F Cl        N(SO.sub.2 CH.sub.3).sub.2                                                                         205.0° C.               175     CF.sub.3                                                                          Cl                                                                              F Cl        N(SO.sub.2 N(CH.sub.3).sub.2).sub.2                                                                149.0-153.0° C.         176     CF.sub.3                                                                          Cl                                                                              F Cl        NEt.sub.2            nD, 1.5262 (25°                                                        C.)                            177     CF.sub.3                                                                          Cl                                                                              F Cl        NH.sub.2             96.0-98.0° C.           178     CF.sub.2 H                                                                        Cl                                                                              F Cl        NH.sub.2             110.0-111.5° C.         179     CF.sub.3                                                                          Cl                                                                              F Cl        NHCH(CH.sub.3).sub.2 nD, 1.5361 (25°                                                        C.)                            180     CF.sub.3                                                                          Cl                                                                              F Cl        NHCH(CH.sub.3)CO.sub.2 Et                                                                          55.0-57.0° C.           181     CF.sub.3                                                                          Cl                                                                              F Cl        NHCH(CH.sub.3)CO.sub.2 H                                                                           167.0-169.0° C.         182     CF.sub.3                                                                          Cl                                                                              F Cl        NHCH(CH.sub.3)CONHCH.sub.3                                                                         134.0-135.0° C.         183     CF.sub.3                                                                          Cl                                                                              F Cl        NHCH.sub.2 CHCH.sub.2                                                                              nD, 1.5483 (25°                                                        C.)                            184     CF.sub.3                                                                          Cl                                                                              F Cl        NHCH.sub.2 CO.sub.2 Et                                                                             114.0-116.0° C.         185     CF.sub.3                                                                          Cl                                                                              F Cl        NHCH.sub.2 CO.sub.2 H                                                                              176.0-182.0° C.         186     CF.sub.3                                                                          Cl                                                                              F Cl        NHCH.sub.2 CCH       73.0° C.                187     CF.sub.3                                                                          Cl                                                                              F Cl        NHCH.sub.3           nD, 1.5509 (25°                                                        C.)                            188     CF.sub.3                                                                          Cl                                                                              F Cl        NHCO.sub.2 Et        74.0-76.0° C.           189     CF.sub.3                                                                          Cl                                                                              F Cl        NHCOCF.sub.3         137.0-138.0° C.         190     CF.sub.3                                                                          Cl                                                                              F Cl        NHCOCH.sub.2 CO.sub.2 CH.sub.3                                                                     155.0° C.               191     CF.sub.3                                                                          Cl                                                                              F Cl        NHCOCH.sub.2 OCH.sub.3                                                                             163.0-165.0° C.         192     CF.sub.3                                                                          Cl                                                                              F Cl        NHPO(OEt).sub.2      84.0-87.0° C.           193     CF.sub.3                                                                          Cl                                                                              F Cl        NHSO.sub.2 CF.sub. 3 300.0° C.               194     CF.sub.3                                                                          Cl                                                                              F Cl        NHSO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                              81.0° C.                195     CF.sub.3                                                                          Cl                                                                              F Cl        NHSO.sub.2 CH.sub.2 CH.sub.3                                                                       112.0° C.               196     CF.sub.3                                                                          Cl                                                                              F Cl        NHSO.sub.2 CH.sub.3  108.0° C.               197     CF.sub.3                                                                          Cl                                                                              F Cl        NO.sub.2             102.0-104.0° C.         198     CF.sub.2 H                                                                        Cl                                                                              F Cl        NO.sub.2             91-92.5° C.             199     CF.sub.3                                                                          Cl                                                                              F Cl        O(CH.sub.2).sub.5 CO.sub.2 Et                                                                      nD, 1.5077 (25°                                                        C.)                            200     CF.sub.3                                                                          Cl                                                                              F Cl        O(CH.sub.2).sub.5 CO.sub.2 H                                                                       nD, 1.5174 (25°                                                        C.)                            201     CF.sub.3                                                                          Cl                                                                              F Cl        O(CH.sub.2).sub.5 CONHCH.sub.2 CH.sub.2                                                            62.0-64.0° C.           202     CF.sub.3                                                                          Cl                                                                              F Cl        O(CH.sub.2).sub.5 CONHCH.sub.3                                                                     118.0-120.0° C.         203     CF.sub.3                                                                          Cl                                                                              F Cl        O-(2-chloro-4-trifluoromethyl)phenyl                                                               nD, 1.5356 (25°                                                        C.)                            204     CF.sub.3                                                                          Cl                                                                              F Cl        O-(2-nitro-4-trifluoromethylphenyl)                                                                119.0° C.               205     CF.sub.3                                                                          Cl                                                                              F Cl        O-(4-trifluoromethyl)phenyl                                                                        nD, 1.5275 (25°                                                        C.)                            206     CF.sub.3                                                                          Cl                                                                              F Cl        O-(p-nitrophenyl)    nD, 1.5796 (25°                                                        C.)                            207     CF.sub.3                                                                          Cl                                                                              F Cl        O-n-dodecyl          nD, 1.4985 (25°                                                        C.)                            208     CF.sub.3                                                                          Cl                                                                              F Cl        O-n-hexyl            nD, 1.5104 (25°                                                        C.)                            209     CF.sub.2 H                                                                        Cl                                                                              F Cl        OC(CH.sub.3).sub.2 CH.sub.2 Cl                                                                     nD, 1.5210 (25°                                                        C.)                            210     CF.sub.3                                                                          Cl                                                                              F Cl        OC(CH.sub.3).sub.3   nD, 1.5128 (25°                                                        C.)                            211     CF.sub.3                                                                          Cl                                                                              F Cl        OCF.sub.2 H          45.0° C.                212     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(CH.sub.2 CH.sub.3)CO.sub.2 Et                                                                  nD, 1.4309 (25°                                                        C.)                            213     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(CH.sub.2 CH.sub.3)CO.sub.2 H                                                                   139.0-140.0° C.         214     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(CH.sub.2 CH.sub.3)CONHCH.sub.3                                                                 152.0° C.               215     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(CH.sub.3)(2-(4,5-dihydooxazolyl))                                                              nD, 1.5336 (25°                                                        C.)                            216     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(CH.sub.3).sub.2  nD, 1.5169 (25°                                                        C.)                            217     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(CH.sub.3)CCH     59.5-61.5° C.           218     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(CH.sub.3)CH.sub.2 OCH.sub.3                                                                    clear oil                      219     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.2 Cl                                                          nD, 1.5168 (25°                                                        C.)                            220     CF.sub. 3                                                                         Cl                                                                              F Cl        OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.3 CH.sub.3                                                    nD, 1.5005 (25°                                                        C.)                            221     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(CH.sub.3)CO.sub.2 (CH.sub.2).sub.4 Cl                                                          nD, 1.5155 (25°                                                        C.)                            222     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(CH.sub.3)CO.sub.2Na.sup.+                                                                      51.0-60.0° C.           223     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(CH.sub.3)CO.sub.2 CH(CH.sub.3).sub.2                                                           clear, colorless oil           224     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(CH.sub.3)CO.sub.2 CH(CH.sub.3)CH.sub.2                                    CH.sub.3             nD, 1.5031 (25°                                                        C.)                            225     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(CH.sub.3)CO.sub.2 CH.sub.2 CH(CH.sub.3).sub.                              2                    nD, 1.5037 (25°                                                        C.)                            226     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(CH.sub.3)CO.sub.2 CH.sub.2 CO.sub.2                                                            nD, 1.5061 (25°                                                        C.)                            227     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(CH.sub.3)CO.sub.2 CH.sub.2 OCH.sub.3                                                           nD, 1.5120 (25°                                                        C.)                            228     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(CH.sub.3)CO.sub.2 CH.sub.3                                                                     nD, 1.5175 (25°                                                        C.)                            229     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(CH.sub.3)CO.sub.2 Et                                                                           nD, 1.5106 (25°                                                        C.)                            230     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(CH.sub.3)CO.sub.2 H                                                                            150.0-151.0°  C.        231     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(CH.sub.3)CO.sub.2 t-butyl                                                                      nD, 1.4999 (25°                                                        C.)                            232     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(CH.sub.3)CON(CH.sub.3).sub.2                                                                   lt. yellow oil                 233     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(CH.sub.3)CONH.sub.2                                                                            152.0° C.               234     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(CH.sub.3)CONHCH.sub.2 CH.sub.2 Cl                                                              104.0° C.               235     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(CH.sub.3)CONHCH.sub.2 CH.sub.2 OH                                                              131.0° C.               236     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(CH.sub.3)CONHCH.sub.2 CO.sub.2 CH.sub.3                                                        111.0-112.0° C.         237     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(CH.sub.3)CONHCH.sub.3                                                                          134.5-135.5° C.         238     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(CH.sub.3)CONHSO.sub.2 CH.sub.3                                                                 159.0° C.               239     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(CH.sub.3)COOCH.sub.2 CH.sub.2 OCH.sub.2                                   CH.sub.2 OMe         nD, 1.5047 (25°                                                        C.)                            240     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(CH.sub.3)CN      nD, 1.5223 (25°                                                        C.)                            241     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(Et)CO.sub.2 CH(CH.sub.3).sub.2                                                                 nD, 1.5026 (25°                                                        C.)                            242     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(Et)CO.sub.2 CH.sub.3                                                                           nD, 1.5127 (25°                                                        C.)                            243     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(Et)CO.sub.2 n-butyl                                                                            nD, 1.4983 (25°                                                        C.)                            244     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(Et)CO.sub.2 t-butyl                                                                            63.0-65.0° C.           245     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(Et)CONH.sub.2    153.0° C.               246     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(Et)CN            nD, 1.5167 (25°                                                        C.)                            247     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(OCH.sub.3)CO.sub.2 CH.sub.3                                                                    nD, 1.5174 (25°                                                        C.)                            248     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(OCH.sub.3)CO.sub.2 H                                                                           lt. yellow oil                 249     CF.sub.3                                                                          Cl                                                                              F Cl        OCH(OCH.sub.3)CONHCH.sub.3                                                                         96.0° C.                250     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 (1,3-DIOXOLAN-2-YL)                                                                      102.5-104.5° C.         251     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 (2-pyridyl)                                                                              122-123° C. (dec)       252     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 (5-(2-chloro)thiophene)                                                                  78-80° C.               253     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 (OXIRANYL) 85.5-86.5° C.           254     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 (TETRAHYDRO-2H-PYRAN-2-YL)                                                               88.5-90.0° C.           255     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 C(CH.sub.3).sub.2 CO.sub.2 CH.sub.3                                                      nD, 1.5087 (25°                                                        C.)                            256     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 C(CH.sub.3).sub.2 CONHCH.sub.3                                                           viscous oil                    257     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 C(Et)NOCH.sub.2 CO.sub.2 Et                                                              nD, 1.5147 (25°                                                        C.)                            258     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 C(Et)NOCH.sub.2 CO.sub.2 H                                                               128.0° C.               259     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 C(Et)NOCH.sub.2 CONH.sub.2                                                               173.0° C.               260     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 C(Et)NOCH.sub.3                                                                          nD, 1.5216 (25°                                                        C.)                            261     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CCH        89.5-91.0° C.           262     CF.sub.3                                                                          Br                                                                              F Cl        OCH.sub.2 CCH        107.0° C.               263     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CF.sub.3   68.0° C.                264     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CH(OCH.sub.3).sub.2                                                                      62.0° C.                265     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CH.sub.2 (1,3-DIOXAN-2-YL)                                                               74.0-75.0° C.           266     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CH.sub.2 Br                                                                              nD, 1.5470 (25°                                                        C.)                            267     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.                                                                nD, 1.5153 (25°                                                        C.)                            268     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                              nD, 1.5175 (25°                                                        C.)                            269     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CH.sub.2 F 103.0° C.               270     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CH.sub.2 OCH.sub.3                                                                       93.0-94.0° C.           271     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CH.sub.2 SCH(CH.sub.3)CO.sub.2                                                           nD, 1.5275 (25°                                                        C.)                            272     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CH.sub.2 SCH.sub.2 CO.sub.2 Et                                                           nD, 1.5321 (25°                                                        C.)                            273     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CH.sub.2 SCH.sub.3                                                                       nD, 1.5464 (25°                                                        C.)                            274     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CH.sub.2 SO.sub.2 CH.sub.3                                                               clear oil                      275     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CH.sub.2 SOCH.sub.3                                                                      87.0° C.                276     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CH.sub.3   80.0° C.                277     CF.sub.3                                                                          Br                                                                              F Cl        OCH.sub.2 CHCH.sub.2 52.5° C.                278     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CHCH.sub.2 76.0° C.                279     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CO.sub.2(CH.sub.3).sub.2 CHNH.sub.3.su                              p. +                 123.0-125.0° C.         280     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CO.sub.2Na.sup.+                                                                         250.0° C.               281     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CO.sub.2 -cyclohexyl                                                                     150.0° C.               282     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CO.sub.2 CH(CH.sub.3).sub.2                                                              134.0-135.0° C.         283     CF.sub.2 H                                                                        Cl                                                                              F Cl        OCH.sub.2 CO.sub.2 CH(CH.sub.3).sub.2                                                              129.0-130.0° C.         284     C.sub.2 F.sub.5                                                                   H F Cl        OCH.sub.2 CO.sub.2 CH(CH.sub.3).sub.2                                                              91-92° C.               285     CF.sub.2 Cl                                                                       Cl                                                                              F Cl        OCH.sub.2 CO.sub.2 CH(CH.sub.3).sub.2                                                              98° C.                  286     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CO.sub.2 CH(CH.sub.3)CH.sub.2                                       CH.sub.3             101.0-103.0° C.         287     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CO.sub.2 CH.sub.2 CH(CH.sub.3)CH.sub.2                               CH.sub.3            96.0° C.                288     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CO.sub.2 CH.sub.2 CH.sub.2 CH(CH.sub.3                              ).sub.2              128° C.                 289     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CO.sub.2 CH.sub.3                                                                        108.0-110.0° C.         290     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CO.sub.2 Et                                                                              130.0-131.0° C.         291     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CO.sub.2 H 174.0° C.               292     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CO.sub.2 n-butyl                                                                         96.0-98.0° C.           293     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CO.sub.2 n-pentyl                                                                        91.0-93.0° C.           294     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CO.sub.2 t-butyl                                                                         127.0° C.               295     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 COCH.sub.2 CH.sub.3                                                                      93.0° C.                296     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CONH.sub.2 191.0° C.               297     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CONHCH(CH.sub.3).sub.2                                                                   130.0° C.               298     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CONHCH.sub.3                                                                             144.0-145.0° C.         299     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CONHN(CH.sub.3).sub.2                                                                    146.0-148.0° C.         300     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 COSCH(CH.sub.3).sub.2                                                                    96.0-97.0° C.           301     CF.sub.3                                                                          H F Cl        OCH.sub.2 CCH        113.0° C.               302     CF.sub.2 H                                                                        Cl                                                                              F Cl        OCH.sub.2 CCH        68.0-69.0° C.           303     CF.sub.2 Cl                                                                       Cl                                                                              F Cl        OCH.sub.2 CCH        nD, 1.5544 (24°                                                        C.)                            304     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CN         98.0° C.                305     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 OCH.sub.2 CH.sub.2 F                                                                     nD, 1.5150 (25°                                                        C.)                            306     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3                                                             nD, 1.5134 (25°                                                        C.)                            307     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 OCH.sub.2 CCH                                                                            nD, 1.5275 (25°                                                        C.)                            308     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 OCH.sub.3  54.5-55.0° C.           309     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 SCH.sub.3  78.0-79.0° C.           310     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 SO.sub.2 CH.sub.3                                                                        137.0° C.               311     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 SOCH.sub.3 109.0-111.0° C.         312     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.3            70.0-71.0° C.           313     CF.sub.3                                                                          Br                                                                              F Cl        OCH.sub.3            85.0-86.0° C.           314     CF.sub.2 H                                                                        Cl                                                                              F Cl        OCH.sub.3            128.0-130.0° C.         315     CF.sub.2 Cl                                                                       Cl                                                                              F Cl        OCH.sub.3            nD, 1.6399 (26°                                                        C.)                            316     CF.sub.3                                                                          Cl                                                                              F Cl        OCHCH.sub.2          57.0° C.                317     CF.sub.3                                                                          Cl                                                                              F Cl        OCHFCO.sub.2 CH(CH.sub.3).sub.2                                                                    96.0° C.                318     CF.sub.3                                                                          Cl                                                                              F Cl        OCHFCO.sub.2 Et      60.0° C.                319     CF.sub.3                                                                          Cl                                                                              F Cl        OCHFCO.sub.2 H       116.0° C.               320     CF.sub.3                                                                          Cl                                                                              F Cl        OCHFCOSCH(CH.sub.3).sub.2                                                                          65.0° C.                321     CF.sub.3                                                                          Cl                                                                              F Cl        OCOCH.sub.2 Cl       nD, 1.5299 (25°                                                        C.)                            322     CF.sub.3                                                                          Cl                                                                              F Cl        OCOCH.sub.2 OCH.sub.3                                                                              76.0-78.0° C.           323     CF.sub.3                                                                          Cl                                                                              F Cl        OCOCH.sub.3          53.0-55.0° C.           324     CF.sub.3                                                                          Cl                                                                              F Cl        OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.2                               CH.sub.2 OMe         nD, 1.5111 (25°                                                        C.)                            325     CF.sub.3                                                                          Cl                                                                              F Cl        OH                   123.0-126.0° C.         326     CF.sub.3                                                                          Br                                                                              F Cl        OH                   83.0° C.                327     CF.sub.3                                                                          H F Cl        OH                   131.0° C.               328     CF.sub.2 H                                                                        Cl                                                                              F Cl        OH                   113.0-114.0° C.         329     CF.sub.2 Cl                                                                       Cl                                                                              F Cl        OH                   107- 109° C.            330     CF.sub.3                                                                          Cl                                                                              F Cl        OSO.sub.2 CH.sub.3   64.0-65.5° C.           331     CF.sub.3                                                                          Cl                                                                              F Cl        OSO.sub.2 n-propyl   nD, 1.5213 (25°                                                        C.)                            332     CF.sub.2 H                                                                        Cl                                                                              F Cl        Ot-butyl             nD, 1.5276 (25°                                                        C.)                            333     CF.sub.3                                                                          Cl                                                                              F Cl        SCF.sub.2 H          nD, 1.5321 (25°                                                        C.)                            334     CF.sub.3                                                                          Cl                                                                              F Cl        SCH(CH.sub.3).sub.2  clear oil                      335     CF.sub.3                                                                          Cl                                                                              F Cl        SCH(CH.sub.3)CO.sub.2 Et                                                                           nD, 1.5345 (25°                                                        C.)                            336     CF.sub.3                                                                          Cl                                                                              F Cl        SCH.sub.2 CH.sub.2 OCH.sub.3                                                                       57.0° C.                337     CF.sub.3                                                                          Cl                                                                              F Cl        SCH.sub.2 CO.sub.2 CH(CH.sub.3).sub.2                                                              nD, 1.5358 (25°                                                        C.)                            338     CF.sub.3                                                                          Cl                                                                              F Cl        SCH.sub.2 CO.sub.2 Et                                                                              63.0-64.0° C.           339     CF.sub.3                                                                          Cl                                                                              F Cl        SCH.sub.2 CO.sub.2 H 128.0° C.               340     CF.sub.3                                                                          Cl                                                                              F Cl        SCH.sub.2 CONH.sub.2 167.0° C.               341     CF.sub.3                                                                          Cl                                                                              F Cl        SCH.sub.2 CCH        98.0° C.                342     CF.sub.3                                                                          Cl                                                                              F Cl        SCH.sub.3            89.0-90.0° C.           343     CF.sub.3                                                                          Cl                                                                              F Cl        SH                   56.0-58.0° C.           344     CF.sub.3                                                                          Cl                                                                              F Cl        SO.sub.2 (1-pyrazolyl)                                                                             155.0° C.               345     CF.sub.3                                                                          Cl                                                                              F Cl        SO.sub.2 CH(CH.sub.3).sub.2                                                                        132.0° C.               346     CF.sub.3                                                                          Cl                                                                              F Cl        SO.sub.2 Cl          116.0-117.0° C.         347     CF.sub.3                                                                          Cl                                                                              F Cl        SO.sub.2 N(CH.sub.3).sub.2                                                                         118.0° C.               348     CF.sub.3                                                                          Cl                                                                              F Cl        SO.sub.2 NHCH.sub.3  113.0° C.               349     CF.sub.3                                                                          Cl                                                                              F Cl        SOCH(CH.sub.3).sub.2 119.0° C.               350     CF.sub.3                                                                          Cl                                                                              F Cl        trans-CHC(CH.sub.3)CO.sub.2 H                                                                      213° C.                 351     CF.sub.3                                                                          Cl                                                                              F Cl        trans-CHCHCO.sub.2 H 209° C.                 352     CF.sub.3                                                                          Cl                                                                              F F         H                    nD, 1.6284 (25°                                                        C.)                            353     CF.sub.3                                                                          Cl                                                                              F F         NH.sub.2             82.0° C.                354     CF.sub.3                                                                          Cl                                                                              F F         Cl                   50.0-51.0° C.           355     CF.sub.3                                                                          Cl                                                                              F F         NO.sub.2             90.5-91.5° C.           356     CF.sub.3                                                                          Cl                                                                              F F         NHCOCH.sub.3         115.0-116.0° C.         357     CF.sub.3                                                                          Cl                                                                              F F         N(SO.sub.2 CH.sub.3).sub.2                                                                         176.5° C.               358     CF.sub.3                                                                          Cl                                                                              F F         NHSO.sub.2 CH.sub.3  163.0-164.0° C.         359     CF.sub.3                                                                          Cl                                                                              F F         NHCOCH.sub.2 OCH.sub.3                                                                             152.0-154.0° C.         360     CF.sub.3                                                                          Cl                                                                              H OCH.sub.3 NO.sub.2             114.0-115.0° C.         361     CF.sub.3                                                                          Cl                                                                              F H         F                    nD, 1.4977 (25°                                                        C.)                            362     CF.sub.3                                                                          Br                                                                              F H         F                    nD, 1.6267 (25°                                                        C.)                            363     CF.sub.3                                                                          Cl                                                                              F H         OC(CH.sub.3).sub.2 CH.sub.2 Cl                                                                     nD, 1.5145 (25°                                                        C.)                            364     CF.sub.2 H                                                                        Cl                                                                              F H         F                    nD, 1.5218 (25°                                                        C.)                            365     CF.sub.2 H                                                                        Br                                                                              F H         F                    61.5° C.                366     CF.sub.3                                                                          Cl                                                                              F NH.sub.2  OCH.sub.3            62.5-63.5° C.           367     CF.sub.3                                                                          Cl                                                                              F NH.sub.2  OCH.sub.2 CH.sub.2 F 135.0° C.               368     CF.sub.3                                                                          Cl                                                                              F NH.sub.2  OEt                  136.0° C.               369     CF.sub.3                                                                          Cl                                                                              F NH.sub.2  OCH.sub.2 CCH        72.0° C.                370     CF.sub.3                                                                          Cl                                                                              F NH.sub.2  OCH(CH.sub.3)CCH     nD, 1.5450 (25°                                                        C.)                            371     CF.sub.3                                                                          H F NH.sub.2  OCH.sub.3            121.5-123.0° C.         372     CF.sub.3                                                                          Br                                                                              F NH.sub.2  OCH.sub.3            85.0-86.0°  C.          373     CF.sub.3                                                                          Cl                                                                              F NH.sub.2  OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.2                               CH.sub.2 OMe         nD, 1.5254 (25°                                                        C.)                            374     CF.sub.3                                                                          Cl                                                                              F NH.sub.2  F                    84.0-86.0° C.           375     CF.sub.3                                                                          Cl                                                                              F NH.sub.2  OC(CH.sub.3).sub.3   light yellow oil               376     CF.sub.3                                                                          Cl                                                                              F NH.sub.2  N(CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.3                                                              nD, 1.5352 (25°                                                        C.)                            377     CF.sub.3                                                                          Cl                                                                              F NH.sub.2  NEt.sub.2            nD, 1.5321 (25°                                                        C.)                            378     CF.sub.3                                                                          Cl                                                                              F NH.sub.2  4-MORPHOLINYL        165.0-166.0° C.         379     CF.sub.3                                                                          Cl                                                                              F NH.sub.2  N(COCH.sub.3)CH(CH.sub.3).sub.2                                                                    178.0° C.               380     CF.sub.3                                                                          Cl                                                                              F NH.sub.2  OCH.sub.2 CH.sub.2 SCH.sub.3                                                                       nD, 1.5591 (25°                                                        C.)                            381     CF.sub.2 H                                                                        Cl                                                                              F NH.sub.2  Ot-butyl             nD, 1.5443 (25°                                                        C.)                            382     CF.sub.3                                                                          Cl                                                                              F NH.sub.2  OCH.sub.2 CF.sub.3   66.0° C.                383     CF.sub.3                                                                          Cl                                                                              F NH.sub.2  NHCH.sub.2 CHCH.sub.2                                                                              112.0° C.               384     CF.sub.3                                                                          Cl                                                                              F OCH.sub.2 CCH                                                                           NO.sub.2             142.0° C.               385     CF.sub.3                                                                          Cl                                                                              F OCH.sub.2 CCH                                                                           NH.sub.2             94.0-96.0° C.           386     CF.sub.3                                                                          Cl                                                                              F OCH.sub.2 CO.sub.2 Et                                                                   NO.sub.2             95.0-96.0° C.           387     CF.sub.3                                                                          Cl                                                                              F OCH.sub.3 NO.sub.2             116.0° C.               388     CF.sub.3                                                                          H F NO.sub.2  F                    80.0-81.0° C.           389     CF.sub.3                                                                          Cl                                                                              F NO.sub.2  F                    nD, 1.5276 (25°                                                        C.)                            390     CF.sub.3                                                                          Cl                                                                              F NO.sub.2  OCH.sub.3            115.0-116.0° C.         391     CF.sub.3                                                                          Cl                                                                              F NO.sub.2  OCH.sub.2 CH.sub.2 F 134° C.                 392     CF.sub.3                                                                          Cl                                                                              F NO.sub.2  OCH.sub.2 CH.sub.3   99.0° C.                393     CF.sub.3                                                                          Cl                                                                              F NO.sub.2  SCH.sub.2 CO.sub.2 Et                                                                              79.0° C.                394     CF.sub.3                                                                          Cl                                                                              F NO.sub.2  OCH.sub.2 CCH        105.0° C.               395     CF.sub.3                                                                          Cl                                                                              F NO.sub.2  OCH(CH.sub.3)CCH     107.5-108.0° C.         396     CF.sub.3                                                                          Br                                                                              F NO.sub.2  F                    45.5° C.                397     CF.sub.3                                                                          Br                                                                              F NO.sub. 2 OCH.sub.3            144.5-145.5° C.         398     CF.sub.3                                                                          H F NO.sub.2  OCH.sub.3            140.0-141.5° C.         399     CF.sub.3                                                                          Cl                                                                              F NO.sub.2  OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.2                               CH.sub.2 OMe         nD, 1.5188 (25°                                                        C.)                            400     CF.sub.3                                                                          Cl                                                                              F NO.sub.2  OCH.sub.2 CO.sub.2 Et                                                                              104.0° C.               401     CF.sub.3                                                                          Cl                                                                              F NO.sub.2  OC(CH.sub.3).sub.3   80.0° C.                402     CF.sub.3                                                                          Cl                                                                              F NO.sub.2  N(CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.3                                                              nD, 1.5534 (25°                                                        C.)                            403     CF.sub.3                                                                          Cl                                                                              F NO.sub.2  NHCH(CH.sub.3).sub.2 100.0° C.               404     CF.sub.3                                                                          Cl                                                                              F NO.sub.2  NEt.sub.2            nD, 1.5387 (25°                                                        C.)                            405     CF.sub.3                                                                          Cl                                                                              F NO.sub.2  4-MORPHOLINYL        136.0-137.0° C.         406     CF.sub.3                                                                          Cl                                                                              F NO.sub.2  N(COCH.sub.3)CH(CH.sub.3).sub.2                                                                    123.0° C.               407     CF.sub.3                                                                          Cl                                                                              F NO.sub.2  SCH(CH.sub.3)CO.sub.2 Et                                                                           nD, 1.5543 (25°                                                        C.)                            408     CF.sub.3                                                                          Cl                                                                              F NO.sub.2  OH                   86.0° C.                409     CF.sub.3                                                                          Cl                                                                              F NO.sub.2  NHCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                             109.0° C.               410     CF.sub.3                                                                          Cl                                                                              F NO.sub.2  OCH.sub.2 COCH.sub.2 CH.sub.3                                                                      103.0° C.               411     CF.sub.3                                                                          Cl                                                                              F NO.sub.2  OCH(CH.sub.3)CH.sub.2 OCH.sub.3                                                                    nD, 1.5263 (25°                                                        C.)                            412     CF.sub.3                                                                          Cl                                                                              F NO.sub.2  OCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                              67.0° C.                413     CF.sub.3                                                                          Cl                                                                              F NO.sub.2  N(COCF.sub.3)CH.sub.2 CH.sub.2 CH.sub.2                                       OCH.sub.3            105.0° C.               414     CF.sub.2 H                                                                        Cl                                                                              F NO.sub.2  F                    80.0° C.                415     CF.sub.2 H                                                                        Cl                                                                              F NO.sub.2  OCH.sub.3            161.0° C.               416     CF.sub.3                                                                          Cl                                                                              F NO.sub.2  OCH.sub.2 CH.sub.2 SCH.sub.3                                                                       nD, 1.5587 (25°                                                        C.)                            417     CF.sub.2 H                                                                        Br                                                                              F NO.sub.2  F                    83.0-85.0° C.           418     CF.sub.2 H                                                                        Br                                                                              F NO.sub.2  OCH.sub.3            154.0-156.0° C.         419     CF.sub.2 H                                                                        Cl                                                                              F NO.sub.2  Ot-butyl             71.0-73.0° C.           420     CF.sub.3                                                                          Cl                                                                              F NO.sub.2  OCH.sub.2 CF.sub.3   108.0-109.0° C.         421     CF.sub.3                                                                          Cl                                                                              F NO.sub.2  NHCH.sub.2 CHCH.sub.2                                                                              54.0-56.0° C.           422     CF.sub.3                                                                          Cl                                                                              F NO.sub.2  N(COCF.sub.3)CH.sub.2 CHCH.sub.2                                                                   91.0° C.                423     CF.sub.3                                                                          Cl                                                                              F OCH.sub.3 NH.sub.2             light yellow oil               424     CF.sub.3                                                                          Cl                                                                              F OCH.sub.3 Cl                   88.0° C.                425     CF.sub.3                                                                          Cl                                                                              F OCH.sub.3 NHCOCH.sub.2 CO.sub.2 CH.sub.3                                                                     111.0° C.               426     CF.sub.3                                                                          Cl                                                                              F OCH.sub.3 NHCOCH(CH.sub.3).sub.2                                                                             134.0° C.               427     CF.sub.3                                                                          Cl                                                                              F OCH.sub.3 H                    97.0° C.                428     CF.sub.3                                                                          Cl                                                                              F OCHFCO.sub.2 Et                                                                         NO.sub.2             84.5-85.5° C.           429     CF.sub.3                                                                          Cl                                                                              F OH        NO.sub.2             m.p. 89.0-90.0° C.      430     CF.sub.3                                                                          Cl                                                                              F SCH.sub.2 CO.sub.2 Et                                                                   NO.sub.2             90.0° C.                431     CF.sub.3                                                                          Cl                                                                              H OCH.sub.2 CO.sub.2 Et                                                                   NO.sub.2             88.0° C.                432     CF.sub.3                                                                          Cl                                                                              H H         OCH.sub.3            b.p..sub.0.8 120.0°                                                    C.                             433     CF.sub.3                                                                          Cl                                                                              H H         CF.sub.3             b.p..sub.3.0                                                                  80.0-120.0° C.          434     CF.sub.3                                                                          Cl                                                                              H F         H                    35.5-36.5° C.           __________________________________________________________________________

In Table 6 are listed various other compounds according to Formula Iwhose structures do not conveniently fit into Tables 4 and 5.

    TABLE 6      Analysis (%) Compound # Name Structure  Calc'd Found             435 1H-pyrazole,-4-chloro-3-(6-fluoro-2,-3-dihydro-1,-4-benzoxath     iin-7-yl)-1-methyl-5-(trifluoromethyl)-MP: 93.0      ##STR28##      CHClFNS 44.272.5710.0521.557.949.09 44.342.577.98      436 1H-pyrazole,-4-chloro-3-(6-fluoro-2,-3-dihydro-1,-4-benzoxathiin-7-y     l)-1-methyl-5-(trifluoromethyl)-,-S,-S-dioxideMP:200.0      ##STR29##      CHClFNS 40.582.369.2119.75 7.288.33 40.702.357.26      437 1H-pyrazole,-4-chloro-3-(6-fluoro-2,-3-dihydro-1,-4-benzoxathiin-7-y     l)-1-methyl-5-(trifluoromethyl)-,-S,-oxideMP: 159.0      ##STR30##      CHClFNS 42.342.469.6120.617.608.70 42.542.437.58      438 2H-1,-4-benzothiazin-3(4H)-one,-6-[4-chloro-1-methyl-5-(trifluoromet     hyl)-1H-pyrazol-3-yl]-7-fluoro-4-(2-pyropynyl)-MP: 174.0      ##STR31##      CHClFNS 47.592.508.7818.8210.41 7.94 47.692.5110.36      439 2H-1,-4-benzothiazin-3(4H)-one,-6-[4-chloro-1-methyl-5-(trifluoromet     hyl)-1H-pyrazol-3-yl]-7-fluoro-MP: 220.0      ##STR32##      CHClFNS 42.692.209.6920.7811.498.77 42.732.1911.40      440 1H-pyrazole,-4-chloro-3-[3-(chloromethylene)-6-fluoro-2,-3-dihydro-5     -benzofuranyl]-1-methyl-5-(trifluoromethyl)-MP: 121.0      ##STR33##      CHClFN 45.802.2019.3120.707.63 45.802.367.62      441 1H-imidazo[2,-1-c]-[1,-4]-benzoxazine,-8-[4-chloro-1-methyl-5-(trifl     uoromethyl)-1H-pyrazol-3-yl]-7-fluoro-2,-4-dihydro-MP: 118.0-120.0      ##STR34##      CHClFN 48.082.969.4620.2814.95 48.543.10      442 1H-pyrazole,-4-chloro-3-(7-fluoro-2,-3-dihydro-1,-4-benzoxathiin-6-y     l)-1-methyl-5-(trifluoromethyl)-MP: 125.0      ##STR35##      CHClFNS 44.272.5710.0521.557.949.09 44.302.527.93      443 4H-1,-4-benzoxazine-4-acetic acid,-6-[4-chloro-1-methyl-5-(trifluoro     methyl)-1H-pyrazol-3-yl]-7-fluoro-alpha-methyl-3-oxo-,-ethyl esterMP:     viscous oil      ##STR36##      CHClFN 48.073.597.8816.909.34 48.043.329.62      444 1H-isoindole-1,-3(2H)-dione,-2-[5-[4-chloro-1-methyl-5-(trifluoromet     hyl)-1H-pyrazol-3-yl]-2,-4-difluorophenyl]-4,-5,-6,-7-tetrahydro-MP:     76.0-78.0      ##STR37##      CHClFN 51.192.947.9521.319.43 52.293.309.14      445 2H-1,-4-benzoxazin-3(4H)-one,-6-[4-chloro-1-methyl-5-(trifluoromethy     l)-1H-pyrazol-3-yl]-4-ethyl-7-fluoro-MP: 95.0-97.0      ##STR38##      CHClFN 47.703.209.3920.1211.12 47.513.22      446 2H-1,-4-benzoxazin-3(4H)-one,-6-[4-chloro-1-methyl-5-(trifluoromethy     l)-1H-pyrazol-3-yl]-7-fluoro-4-(2-propynyl)-MP: 142.0-143.0      ##STR39##      CHClFN 49.562.609.1419.6010.84 49.582.6210.85      447 4H-1,-4-benzoxazine-4-acetonitrile,-6-[4-chloro-1-methyl-5-(trifluor     omethyl)-1H-pyrazol-3-yl]-7-fluoro-2,-3-dihydro-3-oxo-MP: 162.0-163.0      ##STR40##      CHClFN 46.352.339.1219.5514.41 46.032.34      448 4H-1,-4-benzoxazine-4-acetamide,-6-[4-chloro-1-methyl-5-(trifluoro-m     ethyl)-1H-pyrazol-3-yl]-7-fluoro-2,-3-dihydro-N-methyl-3-oxo-MP:     223.0-225.0      ##STR41##      CHClFN 45.673.118.4318.0613.32 45.753.10      449 4H-1,-4-benzoxazine-4-acetic acid,-6-[4-chloro-1-methyl-5-(trifluoro     methyl)-1H-pyrazol-3-yl[-7-fluoro-2,-3-dihydro-3-oxo-,-1,-1-dimethylethyl      esterMP: 161.0-162.0      ##STR42##      CHClFN 49.203.917.6416.399.06 49.454.06      450 4H-1,-4-benzoxazine-4-acetic acid,-6-[4-chloro-1-methyl-5-(trifluoro     -methyl)-1H-pyrazol-3-yl]-7-fluoro-3-oxo-,-1-methylethyl esterMP:     176.0-177.0      ##STR43##      CHClFN 48.073.597.8816.909.34  48.253.709.30      451 4H-1,-4-benzoxazine-4-acetic acid,-6-[4-chloro-1-methyl-5-(trifluoro     -methyl)-1H-pyrazol-3-yl]-7-fluoro-2,-3-dihydro-3-oxo-,-ethyl esterMP:     131.0-133.0      ##STR44##      CHClFN 46.863.248.1417.449.64 47.003.24      452 4H-1,-4-benzoxazine-4-acetamide,-6-[4-chloro-1-methyl-5-(trifluoro-m     ethyl-1H-pyrazol-3-yl]-7-fluoro-2,-3-dihydro-3-oxo-MP: 215.0-217.0      ##STR45##      CHClFN 44.302.73 8.7218.6913.78 44.342.73      453 2H-1,-4-benzoxazine-4-acetic acid,-6-[4-chloro-1-methyl-5-(trifluoro     -methyl)-1H-pyrazol-3-yl]-7-fluoro-3,-4-dihydro-3-oxo-MP: 194.0-196.0      ##STR46##      CHClFN 44.192.478.7018.6410.31 44.132.33      454 2H-1,-4-benzoxazin-3(4H)-one,-6-[4-chloro-1-methyl-5-(trifluoro-meth     yl-1H-pyrazol-3-yl]-7-fluoro-4-[(tetrahydro-2H-pyran-2-yl)-methyl]-MP:     133.0-135.0      ##STR47##      CHClFN 50.96 4.057.9216.979.38 51.234.16      455 2H-1,-4-benzoxazin-3(4H)-one,-6-[4-chloro-1-methyl-5-(trifluoro-meth     yl)-1H-pyrazol-3-yl]-7-fluoro-4-(1,-3-dioxolan-2-ylmethyl)-MP: 150.0-151.     5      ##STR48##      CHClFN 46.863.248.1417.449.64 46.813.249.56      456 2H-1,-4-benzoxazin-3(4H)-one,-6-[4-chloro-1-methyl-5-(trifluoro-meth     yl)-1H-pyrazol-3-yl]-7-fluoro-4-(2-propenyl)-MP: 84.0-86.0      ##STR49##      CHClF N 49.313.109.1019.5010.78 49.273.08      457 2H-1,-4-benzoxazin-3(4H)-one,-6-[4-chloro-1-methyl-5-(trifluoro-meth     yl)-1H-pyrazol-3-yl]-4-[2-(1,-3-dioxan-2-yl)-ethyl]-7-fluoro-MP:     125.5-127.5      ##STR50##      CHClFN 49.203.917.6416.399.06 49.443.978.80      458 2H-1,-4-benzoxazin-3(4H)-one,-6-[4-chloro-1-methyl-5-(trifluoro-meth     yl)-1H-pyrazol-3-yl]-7-fluoro-4-(2-methoxyethyl)-MP: 91.5-92.5      ##STR51##      CHClFN 47.133.468.6918.6410.31 47.273.51      459 2H-1,-4-benzoxazin-3(4H)-one,-6-[4-chloro-1-methyl-5-(trifluoro-meth     yl)-1H-pyrazol-3-yl]-7-fluoro-4-(2-pyridinylmethyl)-MP: 137.0-139.0      ##STR52##      CHClFN 51.772.978.0417.2412.71 51.502.9912.57      460 2H-1,-4-benzoxazin-3(4H)-one,-6-[4-chloro-1-methyl-5-(trifluoro-meth     yl)-1H-pyrazol-3-yl]-7-fluoro-4-(methoxymethyl)-MP: 156.6-157.5      ##STR53##      C HClFN 45.763.079.0019.3010.67 45.933.21      461 2H-1,-4-benzoxazin-3(4H)-one,-6-[4-chloro-1-methyl-5-(trifluoro-meth     yl)-1H-pyrazol-3-yl]-7-fluoro-4-methyl-MP: 140.5-141.5      ##STR54##      CHClFN 46.232.779.7520.9011.55 46.242.7111.68      462 2H-1,-4-benzoxazin-3(4H)-one,-6-[4-chloro-1-methyl-5-(trifluoro-meth     yl)-1H-pyrazol-3-yl]-MP: 216.0      ##STR55##      CHClFN 47.082.7410.6917.1812.67 47.042.75 12.66      463 2H-1,-4-benzoxazin-3(4H)-one,-6-[4-chloro-1-methyl-5-(trifluoro-meth     yl)-1H-pyrazol-3-yl]-7-fluoro-MP: 207.0      ##STR56##      CHClFN 44.652.3110.1421.7312.02 44.662.3111.97      464 2H-1,-4-benzoxazin-3(4H)-one,-6-[4-chloro-1-methyl-5-(trifluoro-meth     yl)-1H-pyrazol-3-yl]-7-fluoro-2-methoxy-4-(2-propynyl)-MP: 101.0-103.0      ##STR57##      CHClFN 48.882.908.4918.1910.06 48.953.00       465 2H-1,-4-benzoxazin-3(4H)-one,-6-[4-chloro-1-methyl-5-(trifluoro-met     hyl)-1H-pyrazol-3-yl]-2,-7-difluoro-4-(2-propynyl)-MP: 114.0-116.0      ##STR58##      CHClFN 47.372.248.7423.4210.36 47.552.45      466 4H-1,-4-benzoxazine-4-acetic acid,-6-[4-chloro-1-methyl-5-(tri-fluor     omethyl)-1H-pyrazol-3-yl]-2,-7-difluoro-3-oxo-,-ethyl esterMP: 114.5-116.      ##STR59##      CHClFN 45.002.897.81 20.949.26 45.002.81      467 2H-1,-4-benzoxazin-3(4H)-one,-6-[4-chloro-1-methyl-5-(trifluoro-meth     yl)-1H-pyrazol-3-yl]-2,-7-difluoro-MP: 186.5-187.5      ##STR60##      CHClFN 42.471.929.6425.8411.43 42.612.13      468 2H-1,-4-benzoxazin-3(4H)-one,-6-[4-chloro-1-methyl-5-(trifluoro-meth     yl)-1H-pyrazol-3-yl]-7-fluoro-2-methyl-4-(2-propynyl)-MP: 150.0-151.0      ##STR61##      CHClFN 50.823.018.8218.9210.46  50.763.02      469 2H-1,-4-benzoxazin-3(4H)-one,-6-[4-chloro-1-methyl-5-(trifluoro-meth     yl)-1H-pyrazol-3-yl]-7-fluoro-2-methyl-MP: 187.0-189.0      ##STR62##      CHClFN 46.232.779.7520.9011.55 46.432.80      470 propanoic acid,-2-[4-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyraz     ol-3-yl]-5-fluoro-2-nitrophenoxy]-,-ethyl esterMP: 136.0-138.0      ##STR63##      CHClFN 43.703.218.0617.289.56 43.813.22      471 2H-1,-4-benzoxazin-3(4H)-one,-6-[4-chloro-1-methyl-5-(trifluoro-meth     yl)-1H-pyrazol-3-yl]-2-ethyl-7-fluoro-4-(2-propynyl)-MP: 126.5-127.5      ##STR64##      CHClFN 52.003.398.5318.2810.11 52.003.38      472 2H-1,-4-benzoxazin-3(4H)-one,-6-[4-chloro-1-methyl-5-(trifluoro-meth     yl)-1H-pyrazol-3-yl]-2-ethyl-7-fluoro-MP: 191.0-192.0      ##STR65##      CHClFN 47.703.209.3920.1211.12 47.753.18      473 2H-1,-4-benzoxazin-3(4H)-one,-6-[4-chloro-1-methyl-5-(trifluoro-meth     yl)-1H-pyrazol-3-yl]-7-fluoro-2-phenyl-4-(2-propynyl)- MP: 146.0-147.0      ##STR66##      CHClFN 56.973.047.6416.399.06 56.773.07      474 1H-benzimidazole,-6-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazo     l-3-yl]-5-fluoro-1-(2-propenyl)-2-trifluoromethyl)-MP: 96.0      ##STR67##      CHClFN 45.032.368.3131.1713.13 44.992.2713.18      475 2(1H)-quinoxalinone,-7-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyr     azol-3-yl]-6-fluoro-MP: 250.0      ##STR68##      CHClFN 45.042.0410.2321.9216.16 45.102.0416.16      476 2H-1,-4-benzoxazin-3(4H)-one,-7-[4-chloro-1-methyl-5-(trifluoro-meth     yl)-1H-pyrazol-3-yl]-6-fluoro-MP: 242.0      ##STR69##      CHClFN 44.652.3110.1421.7312.02 44.612.2711.99      477 2H-1,-4-benzothiazin-3(4H)-one,-7-[4-chloro-1-methyl-5-(trifluoro-me     thyl)-1H-pyrazol-3-yl]-6-fluoro-MP: 225.0      ##STR70##      CHClFNS 42.692.209.6920.7811.498.77 42.732.2311.408.79      478 2(1H)-quinoxalinone,-7-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyr     azol-3-yl]-6-fluoro-3,-4-dihydro-MP: 240.0      ##STR71##      CHClFN 44.782.6010.1721.8016.07 44.762.5916.06      479 2H-1,-4-benzoxazin-3(4H)-one,-7-[4-chloro-1-methyl-5-(trifluoro-meth     yl)-1H-pyrazol-3-yl]-6-fluoro-4-(2-propynyl)-MP: 181.0      ##STR72##      CHClFN 49.562.609.1419.6010.84 49.482.5610.95      480 1H-benzimidazole,-5-[4-chloro-1-methyl-5-(trifluoromethyl-1H-pyrazol     -3-yl]-6-fluoro-1-(2-propenyl)-2-(trifluoromethyl)-MP: nD 1.5186     (25°      C.)     ##STR73##      CHClFN 45.032.368.3131.1713.13 45.082.2513.20      481 1H-pyrazole,-4-chloro-3-[3-(chloromethylene)-5-fluoro-2,-3-dihydro-6     -benzofuranyl]-1-methyl-5-(trifluoromethyl)-(Z)-MP: 140.5-142.5      ##STR74##      CHClFN 45.802.2019.3120.707.63 45.642.227.60      482 1H-pyrazole,-4-chloro-3-[3-(chloromethylene)-5-fluoro-2,-3-dihydro-6     -benzofuranyl]-1-methyl-5-(trifluoromethyl)-(E)-MP: 132.0-135.0      ##STR75##      CHClFN 45.802.2019.3120.707.63 45.712.237.63      483 phenol,-2,-4,-6-trichloro-3-[4-chloro-1-methyl-5-(trifluoromethyl)-1     H-pyrazol-3-yl]-,-hemihydrateMP: 122.5      ##STR76##      CHClFN 34.771.3337.3215.00 7.37 33.871.467.14  484 1H-pyrazole-1-acetic     acid,-4-chloro-5-(4-chloro-2-fluoro-5-methyloxyphenyl)-3-(trifluoromethyl     )-,-methyl esterMP: clear glass (bp.sub.0.065 130-150° C.)*      ##STR77##      CHClFN 41.922.5117.6818.956.98 42.012.506.98      485 1H-pyrazole,-3,-3'-[dithiobis(4-chloro-6-fluoro-1,-3-phenylene)-]-bi     s[4-chloro-1-methyl-5-(trifluoromethyl)-MP: 169.0      ##STR78##      CHClFN S 38.391.4620.6022.088.149.32 38.611.558.069.24      486 2(5H)-furanone,-3-[2-chloro-5-[4-chloro-1-methyl-5-(trifluoro-methyl     )-1H-pyrazol-3-yl]-4-fluorophenoxy]-dihydro-MP: nD 1.5352 (25°     C.)      ##STR79##      CHClFN 43.612.4417.1618.396.78 43.582.486.68      487 benzenepropanenitrile,-2-chloro-alpha-[2-chloro-5-]-4-chloro-1-methy     l-5-(trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorophenyl]-5-[4-chloro-1-meth     yl-5-(trifluoromethyl)-1H-pyraxol-3-yl]-4-fluoro-MP: 130.0-134.0      ##STR80##      CHClFN 44.341.9320.9422.4410.34 44.412.0110.36      488 oxazolidine,-2-[2-chloro-5-[4-chloro-1-methyl-5-(trifluoromethyl)-1H     -pyrazol-3-yl]-4-fluorophenyl]-4,-4-dimethyl-MP: 106.0      ##STR81##      CHClFN 46.853.1917.2918.5310.24 46.713.2410.23      489 1H-pyrazole,-4-chloro-3-(4-chloro-2-fluoro-5-methoxyphenyl)-1-(1-met     hylethyl)-5-(trifluoromethyl)-MP: nD 1.5192 (24°      C.)     ##STR82##      CHClFN 45.303.2619.1020.487.55 45.193.277.49      490 1H-pyrazole,-4-chloro-3-[4-chloro-2-fluoro-5-[4-(methoxy-methyl)-1,-     3-dioxolan-2-yl]-phenyl]-1-methyl-5-(trifluoromethyl)-MP: nD 1.5218     (25°      C.)     ##STR83##      CHClFN 44.773.2916.5217.716.53 44.753.326.56      491 acetamide,-N-4-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-y     l]-5-fluoro-2-nitrophenyl]-2,-2,-2-trifluoro-N-2-propenyl-MP: nD 1.5143     (25°      C.)     ##STR84##      CHClFN 40.482.127.4728.0211.80 40.712.1311.70      492 benzenamine,-4-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-y     l]-5-fluoro-2-nitro-N-2-propenyl-MP: 99.0      ##STR85##      CHClFN 44.402.939.3620.0714.79 44.532.9714.76      493 glycine,-N-[4-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol--3-y     l]-5-fluoro-2-nitrophenyl]-,-methyl esterMP: 176.0      ##STR86##      CH ClFN 40.942.708.6318.5013.64 40.962.7513.74      494 butanoic acid,-2-[4-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazo     l-3-yl]-5-fluoro-2-nitrophenoxy]-,-ethyl esterMP: 117.0-118.0      ##STR87##      CHClFN 45.003.553.557.8116.759.26 44.963.48      495 acetic acid,-[4-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-     yl]-5-fluoro-2-nitrophenoxy]-methoxy-,-methyl esterMP: 113.5-114.5      ##STR88##      CHClF N 40.792.748.0317.219.51 40.932.73      496 benzeneacetic acid,-alpha-[4-[4-chloro-1-methyl-5-(trifluoro-methyl)     -1H-pyrazol-3-yl]-5-fluoro-2-nitrophenoxy]-,-methyl esterMP: 160.0-161.0      ##STR89##      CHClFN 49.252.897.2715.588.61 49.162.88      497 1H-pyrazole,-4-chloro-3-[2-fluoro-4-[2-(methylthio)-ethoxy]-5-nitrop     henyl]-1-methyl-5-(trifluoromethyl)-MP: 69.0      ##STR90##      CHClFNS 40.642.928.5718.3710.167.75 40.452.87 10.16  498 acetic     acid,-[4-[4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-5-fluoro     -2-nitrophenoxy]-,-butyl esterMP: 65.0      ##STR91##      CHClFN 45.003.557.8116.759.26 44.973.569.29      499 1H-pyrazole,-4-chloro-3-(2,-4-dimethoxy-5-nitrophenyl)-1-methyl-5-(t     rifluoromethyl)-MP: 158.0      ##STR92##      CHClFN 42.703.039.6915.5911.49 42.773.0411.50      500 cyclopropanecarboxamide,-1-bromo-N-[2-chloro-5-[4-chloro-1-methyl-5-     (trifluoromethyl)-1H-pyrazol-3-yl]-4-fluorophenyl]-MP: 80.0-94.0      ##STR93##      CHBrClFN 37.922.1216.8214.9316.008.85 38.412.268.80      501 1H-pyrazole,-4-chloro-1-(chloromethyl)-3-(2,-4-difluorophenyl)-5-(tr     ifluoromethyl)-MP: nD 1.5096 (25°      C.)     ##STR94##      CHClFN 39.911.5221.4228.698.46 40.031.508.49     *Bulb-to-bulb distillation

PRE-EMERGENCE HERBICIDE TESTS

As noted above, the compounds of this invention have been found to besurprisingly effective as herbicides.

The tests for pre-emergence herbicide activity are conducted as follows:

Topsoil is placed in an aluminum pan and compacted to a depth of 0.95 to1.27 cm from the top of the pan. On the top of the soil is placed apredetermined number of seeds of each of several monocotyledonous anddicotyledonous annual plant species and/or vegetative propagules ofvarious perennial plant species. A known amount of the active ingredientdissolved or suspended in an organic solvent, e.g., acetone, or water ascarrier is then applied directly to the seed bed, which is then coveredwith a layer of untreated topsoil to level fill the pan. Aftertreatment, the pans are moved to a greenhouse bench where they arewatered from below as needed to give adequate moisture for germinationand growth.

Approximately 10-14 days (usually 11 days) after seeding and treating,the pans are observed and the results (% inhibition) are recorded.

Tables 7 and 7A below summarize the results of the pre-emergenceherbicidal activity tests of compounds of this invention in weeds. Theherbicidal rating shown in these tables is the percent inhibition ofeach plant species. The plant species usually regarded as weeds whichare utilized in one set of tests, the data for which are shown in thetables, are identified by letter headings above the columns inaccordance with the following legend:

Yens--Yellow nutsedge

Anbg--Annual bluegrass

Sejg--Seedling johnsongrass

Dobr--Downy Brome

Bygr--Barnyardgrass

Mogl--Morningglory

Cobu--Cocklebur

Vele--Velvetleaf

Inmu--Indian Mustard

Wibw--Wild buckwheat

Where noted in the tables below, the symbol "C" represents 100% controland the symbol "N" indicates that the species was planted, but no dataobtained for one reason or another. Compound Nos. 1-61 are intermediatecompounds and do not appear in Tables 7 and 8 below.

                  TABLE 7                                                         ______________________________________                                        PREEMERGENCE TESTS                                                            % PLANT INHIBITION                                                                                 Y   A   S   D   B   M   C   V   I                                                     W                                                                                e n e o y o o e n i                                                        Cpd.  Rate n b j b g g b l m b                                                No.  kg/ha s g g r r l u e u w                   ______________________________________                                         62          11.21   0   0   30  0   20  30  0   60  20                                                    20                                                                             63  11.21 0 C C C C C 60 C C C                                                64  11.21 10 90 80 90 80 80 10 C C C                                          65 ) 11.21 0 70 70 0 30 20 0 90 N 80                                          66  11.21 0 70 70 0 30 20 0 90 N 80                                           67  11.21 0 40 40 40 0 90 0 80 50 90                                          68 * 11.21 30 0 10 0 10 30 0 40 0 N                                           69  11.21 0 0 0 0 0 30 0 50 0 0                                               70  11.21 0 40 80 20 40 80 20 90 80 80                                        71  11.21 0 90 40 10 0 30 0 60 30 70                                          72  11.21 0 20 60 20 60 40 20 90 90 90                                        73  11.21 0 0 0 0 0 0 0 50 20 0                                               74   1.12 0 10 60 20 20 50 0 90 90 C                                          75  11.21 20 0 50 20 20 90 10 80 30 50                                        76   1.12 0 10 0 10 0 40 20 50 60 C                                           77  11.21 0 80 40 10 30 0 0 30 30 20                                          78  11.21 0 0 0 0 0 0 0 0 0 0                                                 79  11.21 20 90 80 80 80 C 30 C C C                                           80  11.21 0 90 80 70 70 60 60 C 80 90                                         81 ) 11.21 0 60 90 80 60 30 20 90 20 C                                        82  11.21 30 60 C C C C 40 C 80 C                                             83  11.21 20 40 C 90 60 30 40 90 60 90                                         84  11.21 30 C C C C 90 80 C C C                                             85  11.21 0 C C C C C 40 C C C                                                86  11.21 0 0 0 0 0 20 10 90 30 C                                             87  11.21 10 10 30 20 40 70 10 90 70 90                                       88  11.21 10 20 30 10 10 10 20 80 20 C                                        90  11.21 0 10 50 10 10 10 0 20 10 30                                         91   1.12 0 0 0 0 0 90 20 C 90 70                                             92   1.12 0 0 0 0 0 80 20 90 20 80                                            93   1.12 20 C C C C 90 60 C C C                                              95   1.12 20 30 50 20 50 40 20 90 80 C                                        96   1.12 20 C 90 C 80 C 60 C C C                                             97   1.12 20 80 50 80 50 40 90 C 90 C                                         99  11.21 30 80 90 C 90 90 80 C C C                                          100   1.12 0 90 90 C 70 80 20 C C C                                           101   1.12 0 70 80 80 40 80 30 C C 90                                         102   1.12 20 60 90 80 80 C 30 C C C                                          103   1.12 0 20 40 70 20 60 0 50 40 C                                         104   1.12 0 20 80 80 10 80 20 90 80 70                                       105   1.12 20 0 60 40 70 80 10 90 80 80                                       106   1.12 0 30 80 80 80 60 20 80 90 C                                        107   1.12 0 20 40 30 80 C 20 90 80 80                                        108  11.21 20 50 90 C C 90 80 C C C                                           109   1.12 0 20 80 20 90 70 30 90 90 C                                        110   1.12 0 0 0 0 20 70 50 C 80 70                                           111  11.21 60 80 80 70 40 C 90 C C C                                          112  11.21 80 C 90 20 C C 40 C C 90                                           113  11.21 0 10 30 0 80 30 0 80 80 40                                         114  11.21 90 C 90 60 C C 70 C C C                                            115   1.12 0 40 70 70 80 80 20 C C 90                                         116   1.12 0 90 90 80 90 90 50 C 90 C                                         117   1.12 0 C 70 90 C 90 70 C C C                                            118   1.12 0 C 90 C 90 C 80 90 C C                                            119  11.21 70 10 80 80 C C C C C C                                            120   1.12 10 70 80 70 80 80 30 C 90 C                                        121  11.21 70 C 80 70 C C 60 C C C                                            122   1.12 0 20 40 20 80 80 40 C C 70                                         123   1.12 30 0 40 70 30 C 50 C 80 90                                         124  11.21 20 C C C C C C C C C                                               125   1.12 0 C C 90 C 90 30 C C C                                             126   1.12 0 C C C C C 50 C C C                                               127   1.12 0 0 20 0 30 70 20 C 90 C                                           128   1.12 0 0 30 0 0 80 70 C 70 C                                            129   1.12 0 0 60 40 20 C 90 C 90 C                                           130   1.12 20 0 70 30 30 C 90 C C 90                                          131   1.12 20 0 70 30 40 C 80 C 90 C                                          132  11.21 30 60 70 80 90 C 70 C 90 C                                         133   1.12 20 20 80 0 80 70 40 C C 70                                         134   1.12 0 50 40 70 10 20 30 70 60 90                                       135   1.12 0 C C C C 90 90 C C C                                              137   1.12 20 70 50 80 70 C C C C 90                                          138   1.12 20 40 30 90 50 C C C C C                                           142   1.12 0 10 20 70 40 C 60 C 90 50                                         143   1.12 10 10 40 20 20 90 80 C C C                                         144   1.12 10 10 20 10 30 80 C C 80 70                                        145   1.12 60 0 30 20 30 C 70 C C 70                                          146   1.12 20 C C C C C 90 C C C                                              147   1.12 30 0 40 10 40 80 20 C 80 70                                        148   1.12 0 70 50 80 90 C 90 C C C                                           149   1.12 20 0 20 0 20 90 30 C 70 60                                         150   1.12 0 70 90 80 60 40 60 90 80 C                                        151   1.12 0 C C C 90 70 90 90 90 C                                           152   1.12 0 70 20 70 60 90 20 C 90 90                                        153   1.12 30 C C 50 C 90 10 C C 90                                           154   1.12 30 10 C 10 90 C C C C C                                            155   1.12 0 90 90 30 80 90 70 C C C                                          156   1.12 20 20 C 20 90 C 80 C C 90                                          157   1.12 50 C 90 80 C C 80 C C C                                            158   1.12 10 30 80 70 80 C 50 C C 90                                         159 ( 11.21 C 90 V 90 C C C C C C                                             160   1.12 0 20 80 50 30 30 40 40 20 90                                       161  11.21 60 40 90 80 C C C C C C                                            162   1.12 20 80 C 90 70 80 70 90 80 C                                        163  11.21 50 C C C C C C C C C                                               164 + 11.21 10 70 80 C 20 C 40 C C C                                          165  11.21 40 C C C C C C C C C                                               166   1.12 30 70 80 80 40 50 50 90 90 C                                       167 @ 11.21 0 50 80 C 70 50 40 90 C C                                         168  11.21 0 0 0 0 0 30 30 80 30 C                                            169   1.12 0 20 80 C 50 40 30 70 80 90                                        170 @ 11.21 0 30 90 C 80 C 40 C C C                                           171  11.21 20 40 80 50 90 60 40 C 70 80                                       172   1.12 20 30 0 0 20 0 0 30 80 80                                          173   1.12 20 C 60 90 70 60 30 80 80 80                                       174   1.12 0 30 80 60 50 70 30 90 90 90                                       175  11.21 0 80 20 40 70 80 10 80 10 90                                       176  11.21 20 C C C 90 C 80 C C C                                             177  11.21 20 C 90 90 C C 90 C C C                                            179   1.12 0 70 90 90 70 80 80 90 C C                                         180   1.12 0 0 0 40 30 90 80 C 90 C                                           181  11.21 30 C 80 C 90 C C C C C                                             182  11.21 90 C C C C C C C C C                                               183 +  1.12 0 50 80 90 20 70 70 90 90 C                                       184  11.21 0 20 0 20 30 C 60 C C C                                            185  11.21 20 C 80 C C C C C C C                                              186   1.12 0 40 60 C 20 80 70 C 80 C                                          187 +  1.12 0 30 70 50 20 40 40 80 C C                                        188  11.21 20 60 80 70 80 C 80 C 80 C                                         189   1.12 0 0 0 10 0 50 30 80 80 80                                          190   1.12 0 20 20 10 10 C 30 C 90 C                                          191  11.21 0 0 20 30 70 70 40 C 80 C                                          192  11.21 0 C 90 C 90 90 90 C C C                                            193  11.21 50 C 50 60 40 C C C C C                                            194   1.12 20 0 30 20 0 80 30 90 60 80                                        195   1.12 0 0 20 20 50 C 90 C 80 30                                             1.12 0 N 0 N 0 0 0 N N N                                                   196   1.12 50 0 0 20 60 80 50 C C 70                                          197  11.21 0 0 30 30 80 60 80 C C C                                           199   1.12 0 0 20 20 20 70 40 C 80 60                                         200   1.12 0 0 0 0 30 C 80 C 90 60                                            201   1.12 0 0 20 0 30 70 70 C 80 30                                          202   1.12 0 0 20 20 20 60 50 60 70 80                                        204   1.12 0 0 0 0 0 0 0 0 0 0                                                206  11.21 0 0 20 0 10 20 20 0 20 40                                          207 @  1.12 0 0 0 0 0 0 0 0 0 0                                               208   1.12 30 50 80 C 60 60 80 80 70 C                                        209   1.12 0 0 0 0 20 20 0 20 0 0                                             210   1.12 20 20 80 70 40 80 30 80 80 C                                       211   1.12 10 80 C C C C 80 C C C                                             212   1.12 20 30 50 80 70 80 70 C C 90                                        213   1.12 20 90 50 90 C 60 50 C C 80                                         214   1.12 30 80 70 70 90 80 50 C C C                                         215   1.12 0 60 40 20 80 80 30 C C 90                                         216   1.12 30 C C C 90 C 80 C C C                                             217   1.12 20 C C C C C 80 C C C                                              218   1.12 0 50 40 70 80 C 70 C C C                                           219   1.12 30 60 50 60 70 90 90 C C 70                                        220   1.12 50 70 60 70 70 80 90 90 90 60                                      221   1.12 30 30 50 50 20 80 80 80 C 30                                       222   1.12 40 80 30 60 80 70 80 C C C                                         223   1.12 40 60 50 60 60 80 90 C 90 40                                       224   1.12 0 40 70 80 70 60 C C 50 C                                             1.12 0 N N N 0 0 0 N N N                                                   225   1.12 30 90 60 80 60 50 80 C C 60                                        226   1.12 30 20 40 50 50 80 90 90 C 50                                       227   1.12 30 50 50 40 70 80 90 C C 60                                        228   1.12 20 60 50 80 50 80 C 90 C 60                                        229   1.12 60 C C C 90 C 90 C C C                                             230   1.12 20 60 80 60 90 90 60 C C C                                         231   1.12 0 20 40 50 30 0 40 40 20 20                                        232   1.12 40 C 80 70 90 C 30 C C C                                           233   1.12 30 80 70 50 90 90 30 C C C                                         234   1.12 20 40 50 30 40 70 30 C C 90                                        235   1.12 30 90 70 30 C C 30 C C C                                           236   1.12 30 90 90 C 50 C C C C C                                            237   1.12 60 90 90 80 C C 40 C C C                                           238   1.12 50 10 20 20 20 70 C C C 80                                            1.12 40 10 10 0 0 80 C C C 70                                              239   1.12 30 30 50 50 30 80 90 C C 30                                        240   1.12 0 80 90 C 80 C 90 C C C                                            241   1.12 20 C 60 90 60 50 50 C 70 80                                        242   1.12 30 90 30 90 40 80 60 C C 80                                        243   1.12 20 80 30 60 30 60 70 C 90 60                                       244   1.12 30 0 10 50 0 0 0 20 0 10                                           245   1.12 0 60 60 30 80 80 30 90 C C                                         246   1.12 0 90 80 C 70 80 90 90 C C                                          247   1.12 30 20 50 20 50 C 70 C 90 80                                        248   1.12 30 30 20 0 40 90 50 C 90 90                                        249   1.12 60 C 90 80 C C 50 C C C                                            250   1.12 0 30 60 90 80 90 10 C 70 C                                         253   1.12 20 30 60 40 80 90 20 90 90 90                                      254   1.12 0 80 70 80 70 20 30 C 70 C                                         255   1.12 0 0 30 40 0 90 60 90 90 80                                         256   1.12 0 60 60 40 80 80 40 C C C                                          257   1.12 0 10 20 20 0 70 30 90 80 80                                        258   1.12 0 20 40 10 20 80 C 80 C 70                                         259   1.12 0 0 0 0 0 60 N 30 20 0                                             260   1.12 0 20 30 C 20 30 30 40 50 80                                        261  11.21 30 C C C C C C C C C                                               262   1.12 40 C C C C C 80 C C C                                              263   1.12 0 C C C C C C C C C                                                264   1.12 30 60 70 C 80 C 70 C 90 C                                          265   1.12 0 90 80 90 20 20 20 70 60 C                                        266   1.12 30 70 50 C 90 70 40 40 80 C                                        267   1.12 30 60 90 90 70 70 70 90 80 C                                       268   1.12 0 40 60 C 60 70 60 90 80 C                                         269   1.12 20 C C C 90 90 60 C C C                                            270   1.12 30 70 70 C 90 C 60 C C C                                           271   1.12 30 50 80 80 80 80 70 80 80 C                                       272   1.12 40 20 80 70 90 C 70 C C C                                          273   1.12 20 80 70 60 C C 40 C C C                                           274   1.12 0 20 40 20 80 80 0 C C 60                                          275   1.12 20 20 40 20 80 C 70 C C C                                          276   1.12 20 C C C C C 80 C C C                                              277   1.12 20 C C C C 90 50 C C C                                             278   1.12 20 C 90 C 90 C 70 C C C                                            279  11.21 C 90 C C 90 C C C C C                                              280  11.21 90 50 80 40 80 C C C 90 C                                          281   1.12 0 0 0 0 0 40 80 70 20 50                                           282   1.12 40 20 30 20 20 90 30 C 30 90                                       283   1.12 40 20 20 0 0 C C C 70 70                                           286   1.12 0 0 20 20 50 C C C 0 80                                            289   1.12 70 30 70 20 20 90 50 C 40 90                                       290   1.12 80 30 30 20 20 C C C 40 90                                         291   1.12 30 30 40 20 20 C C C 40 C                                          292   1.12 40 20 40 20 20 C 40 80 30 80                                       293   1.12 20 0 20 0 20 C 80 C 0 70                                           294 +  1.12 0 0 20 20 20 70 80 70 0 90                                        295   1.12 0 40 60 50 50 60 30 70 60 C                                        296   1.12 30 0 0 0 30 90 90 C C C                                            297   1.12 0 20 40 60 80 20 10 90 70 90                                       298   1.12 50 30 30 20 80 C 40 C C C                                          299   1.12 0 0 20 20 70 C 80 C C 70                                           300   1.12 20 0 0 0 0 C 80 C 40 50                                            301  11.21 0 0 0 90 20 30 0 40 40 90                                          302   1.12 0 C 90 C C C 90 C C C                                              304   1.12 10 80 80 C 80 C 90 C C C                                           305   1.12 0 90 90 C 90 70 30 C 90 C                                          306   1.12 0 60 40 C 80 80 70 C C C                                           307 @  1.12 30 80 80 C 70 C 90 90 90 C                                        308   1.12 40 C C C C C 80 C C C                                              309   1.12 40 C 90 C C C 80 C C C                                             310   1.12 20 90 70 20 80 C 30 C C C                                          311   1.12 60 C 90 90 C C 60 C C C                                            312  11.21 60 C C C C C C C C C                                               313   1.12 30 C C C C C 90 C C C                                              314   1.12 20 80 90 C 90 C 80 C C C                                           316   1.12 0 C 90 C 90 90 50 C C C                                            317   1.12 10 90 70 60 60 90 C C 80 C                                         318  11.21 70 C 90 C C C C C C C                                              319   1.12 20 80 40 70 30 90 50 C 80 C                                        320   1.12 0 60 40 40 30 C 90 C 80 C                                          321   1.12 20 20 30 80 60 60 20 C 50 C                                        322   1.12 0 20 30 80 30 C 30 C 60 C                                          323   1.12 0 60 70 90 70 80 20 C 50 C                                         324   1.12 20 70 50 70 80 C 30 90 90 C                                        325  11.21 0 90 C C C 90 90 C C C                                             326  11.21 20 C 90 C 90 C 80 C C C                                            327  11.21 0 0 0 0 0 0 0 20 0 0                                               328   1.12 0 10 40 90 0 70 20 C 0 C                                           330   1.12 20 60 80 80 70 80 20 C C C                                         331   1.12 0 30 40 70 20 70 50 80 70 80                                       332   1.12 0 60 80 70 60 80 0 80 70 90                                        333   1.12 0 70 90 C 70 90 40 C C 90                                          334   1.12 0 60 70 80 80 40 40 70 80 C                                        335   1.12 0 0 0 0 0 C C C 90 80                                              336   1.12 0 30 60 80 40 90 60 80 80 90                                       337   1.12 10 0 30 20 70 C 70 C 80 80                                         338   1.12 20 20 20 20 70 C 50 80 80 70                                       339   1.12 30 10 0 0 10 80 90 C 90 90                                         340   1.12 20 80 70 40 80 C C C C 90                                          341 @  1.12 20 C 90 90 70 90 90 C C C                                         342   1.12 30 C C C 90 C 80 C C C                                             343  11.21 0 0 0 20 0 20 0 50 30 80                                           344   1.12 0 0 0 0 0 0 0 60 0 0                                               345   1.12 0 0 20 20 30 20 0 70 50 70                                         346  11.21 30 0 0 0 0 80 30 C C 60                                            347  11.21 0 80 70 70 80 80 30 C 90 80                                        348   1.12 40 60 40 20 80 C C C C 70                                          349   1.12 0 20 60 30 70 30 20 80 70 80                                       352  11.21 20 30 50 40 30 80 60 90 60 80                                      353  11.21 0 80 70 20 50 80 80 C C C                                          354   1.12 0 20 70 30 60 20 20 90 30 C                                        355  11.21 0 0 30 0 20 0 30 80 30 90                                          356  11.21 30 C C 80 90 C 40 C C C                                            357  11.21 20 30 80 40 70 80 20 60 90 70                                      358  11.21 70 60 50 30 80 C 80 C C 70                                         359   1.12 20 0 20 0 40 40 30 90 90 C                                         360  11.21 0 0 0 0 0 0 0 0 0 0                                                361  11.21 0 0 40 60 80 50 0 90 50 80                                         362  11.21 0 50 80 60 50 80 20 90 60 C                                        363  11.21 0 0 40 20 0 0 0 50 0 60                                            364  11.21 0 30 80 80 80 70 20 C 60 90                                        365  11.21 30 70 C C C 90 30 C 70 90                                          366  11.21 20 C C C C 50 50 C 70 C                                            367  11.21 0 0 0 0 0 0 0 0 0 0                                                368  11.21 0 0 0 0 0 0 0 30 0 0                                               369  11.21 0 0 0 0 0 30 0 80 30 80                                            370  11.21 0 0 20 0 0 20 0 30 30 80                                           371  11.21 0 0 0 0 0 0 0 0 0 0                                                372  11.21 0 0 0 0 0 0 0 40 10 0                                              373  11.21 0 0 0 0 0 0 0 0 0 20                                               374  11.21 0 0 30 0 0 0 0 80 30 90                                            375  11.21 0 0 0 0 0 0 0 0 0 0                                                376  11.21 0 0 20 0 0 20 0 70 80 30                                           377  11.21 0 0 60 20 40 20 0 90 80 20                                         378  11.21 0 20 50 0 80 70 0 50 80 30                                         379  11.21 0 0 0 0 0 0 0 30 0 50                                              380  11.21 0 0 0 0 0 20 0 30 0 0                                              381   1.12 0 0 20 0 0 0 0 0 0 0                                               382  11.21 0 0 0 0 0 40 0 70 0 80                                             383  11.21 10 10 0 20 10 50 10 70 70 40                                         11.21 0 0 0 0 0 40 0 60 60 20                                               384  11.21 0 0 0 0 20 0 0 0 30 0                                              385  11.21 0 0 0 0 30 0 0 20 0 0                                              386  11.21 0 0 0 0 40 20 0 80 80 40                                           387  11.21 0 0 0 0 0 0 0 0 0 0                                                388  11.21 0 30 0 0 0 30 10 80 50 80                                          389  11.21 30 C C C C C 70 C C C                                              390  11.21 20 C C C C C 80 C C C                                              391   1.12 20 C C 80 C 70 50 C C C                                            392   1.12 30 C C C C C 60 C C C                                              393   1.12 0 0 20 0 20 80 0 80 20 40                                          394   1.12 10 30 80 90 60 50 40 90 C C                                        395   1.12 10 30 80 C 50 30 40 70 80 C                                        396  11.21 30 C C 90 90 C 70 C C C                                            397   1.12 20 20 80 90 90 50 20 80 80 90                                      398   1.12 0 0 0 0 0 0 0 0 0 0                                                399   1.12 0 0 30 0 80 40 20 70 C 90                                          400  11.21 80 30 30 20 60 0 0 90 80 90                                        401   1.12 30 60 80 40 30 20 80 80 C                                          402   1.12 0 30 60 80 30 0 0 40 50 80                                         403  11.21 20 40 90 90 80 70 80 80 70 C                                       404  11.21 30 60 90 C 70 80 30 90 90 C                                        405  11.21 30 50 90 50 80 70 60 C 80 C                                        406  11.21 20 30 90 40 C 80 60 C C 90                                         407  11.21 40 20 20 20 40 C C C 80 80                                         408 @ 11.21 20 80 70 20 30 70 40 C 80 C                                       409 + 11.21 0 0 40 20 20 40 20 50 N N                                         410 + 11.21 0 30 60 40 60 40 30 60 70 30                                      411   1.12 0 90 C C 80 80 40 90 C C                                           412   1.12 0 20 40 30 50 70 40 60 50 80                                       413  11.21 0 20 60 50 40 40 20 70 40 90                                       414  11.21 20 C 90 60 60 C 20 C C C                                           415   1.12 0 30 80 30 80 40 20 90 90 70                                       416   1.12 10 70 80 20 80 30 60 80 C 30                                       417   1.12 20 0 30 0 0 20 0 60 40 30                                          418   1.12 20 20 70 40 70 30 70 80 60 50                                      419   1.12 0 20 30 30 10 70 20 80 60 80                                       420   1.12 0 20 80 80 70 20 20 60 50 C                                        421  11.21 0 80 90 C 40 C 80 C 90 C                                           422  11.21 0 70 90 C 70 70 40 C 70 C                                          423  11.21 0 0 0 0 0 0 0 50 20 20                                             424  11.21 0 0 40 20 0 0 0 40 0 30                                            425  11.21 0 0 70 20 20 C 40 C C 30                                           426  11.21 0 0 50 10 50 40 0 70 60 70                                         427 ( 11.21 0 0 0 0 0 0 0 0 10 0                                              428  11.21 0 0 0 0 20 30 0 90 70 70                                           429  11.21 0 30 30 10 20 0 0 30 50 10                                         430  11.21 20 0 30 0 0 70 40 60 30 20                                         431  11.21 0 0 0 0 0 0 0 60 20 0                                              432  11.21 0 20 50 70 10 20 10 C 10 90                                        433  11.21 0 0 0 0 0 0 0 0 0 0                                                435  11.21 0 40 60 30 70 C 20 C 90 90                                          + 11.21 N N N 0 0 0 0 0 0 0                                                  436 + 11.21 N N N 0 0 0 0 0 0 0                                                 11.21 20 0 0 0 0 30 0 40 20 10                                              437 + 11.21 0 0 0 0 40 80 30 80 80 60                                         438   1.12 0 30 60 40 30 70 50 80 80 40                                       439   1.12 0 0 0 0 0 80 50 50 60 40                                           440  11.21 0 30 50 70 40 50 20 60 40 C                                        441   1.12 0 40 40 20 80 90 20 C C 70                                         442  11.21 10 60 80 70 C 80 20 C C C                                          443   1.12 0 80 10 50 40 90 80 C 90 C                                         444   1.12 0 30 80 20 30 0 0 0 N N                                            445   1.12 10 C 80 C 80 C C C C C                                             446   1.12 60 C 80 90 80 C C 90 C C                                           447   1.12 30 C 40 80 90 C C C C C                                            448   1.12 80 C 90 80 C C C C C C                                             449 (  1.12 0 60 80 50 60 30 30 70 10 30                                      450   1.12 0 0 10 0 20 80 20 90 10 40                                         451   1.12 20 0 20 20 30 C 70 80 50 70                                        452   1.12 80 C 90 70 C C C C C C                                             453   1.12 0 0 0 0 0 90 20 C 30 80                                            454 (  1.12 0 C 80 80 80 90 80 C C C                                          455   1.12 40 C 90 C 90 C C C C C                                             456   1.12 40 C 80 C 80 C C C C C                                             457   1.12 0 C 70 40 60 C 40 90 90 C                                          458 (  1.12 50 C 90 C 90 C C C C C                                            459   1.12 10 C 60 70 90 C 70 C C C                                           460 (  1.12 20 C 90 C 90 C 70 C C C                                           461   1.12 60 C 90 C 90 C 30 C C C                                            462  11.21 0 0 0 0 60 80 50 90 C C                                            463   1.12 50 30 70 50 80 C 80 C C C                                          464   1.12 0 C 70 80 70 90 30 C C C                                           465  11.21 20 C C C C C C C C C                                               466  11.21 70 0 0 10 0 90 50 C 80 C                                           467  11.21 10 20 10 10 80 0 10 C C 80                                         468   1.12 0 90 50 90 60 80 70 90 C C                                         469   1.12 20 20 20 10 80 70 20 C C C                                            1.12 20 40 0 0 40 80 10 C C C                                              470   1.12 0 0 0 0 0 20 40 20 0 0                                             471  11.21 20 90 80 80 20 30 30 90 80 C                                       472  11.21 0 0 0 0 20 20 10 90 70 50                                          473  11.21 0 0 0 0 0 0 0 10 N 30                                              474  11.21 0 80 C C 90 C 70 C 90 C                                            475  11.21 20 70 60 30 80 C 40 C C C                                          476  11.21 0 0 0 0 0 0 0 0 0 0                                                477  11.21 0 30 0 0 0 0 0 0 0 0                                               478  11.21 30 80 70 40 C C C C C C                                            479  11.21 0 0 0 0 0 0 0 0 0 0                                                480  11.21 0 0 0 0 0 0 0 0 0 0                                                481  11.21 0 40 30 60 20 30 0 70 60 90                                        482  11.21 30 80 60 C 80 C 80 C C C                                           484 @  5.61 0 0 20 0 0 20 0 60 20 20                                          485  11.21 0 20 30 30 0 0 0 30 30 70                                          486   1.12 0 70 60 80 80 90 20 80 C 80                                        487  11.21 0 0 0 0 0 50 0 40 20 0                                             489  11.21 0 90 80 C 30 10 0 10 0 10                                             1.12 0 0 0 0 0 0 0 0 0 0                                                   490   1.12 0 60 50 60 60 70 40 C 80 90                                        491  11.21 0 0 0 0 0 0 0 0 0 0                                                492  11.21 0 0 0 0 0 0 0 0 0 0                                                493  11.21 20 0 0 0 0 0 0 10 20 0                                             494  11.21 0 0 0 0 0 0 0 10 20 10                                             495   1.12 0 0 0 0 0 10 0 10 0 0                                              496   1.12 0 0 0 0 0 0 0 0 0 0                                                497  11.21 0 0 0 0 0 20 0 0 0 0                                               498  11.21 0 0 0 0 80 50 10 C 70 90                                           499  11.21 0 0 0 0 0 0 0 0 0 0                                                501  11.21 20 90 60 90 90 80 20 C 90 40                                          1.12 0 0 0 0 0 0 0 30 20 20                   ______________________________________                                         * Poor germinationWibw.                                                       @ Cocklebur germination eratic                                                + Excessive damping off                                                       (Sejg germination was thin.                                                   ) FREQUENT DAMPING OFFInmu, Wibw                                         

                  TABLE 7A                                                        ______________________________________                                        PREEMERGENCE TESTS                                                            % PLANT INHIBITION                                                                          Y     A    S   D    B   M   C   V    I   W                                    e     n    e   o    y   o   o   e    n   i                      Cpd. Rate     n     b    j   b    g   g   b   l    m   b                      No.  kg/ha    s     g    g   r    r   l   u   e    u   w                      ______________________________________                                         89  11.21    10    0    0   0    0   20  0   90   70  30                      93  1.12     0     0    0   0    0   30  20  20   10  20                      98  1.12     0     0    70  60   30  80  20  90   70  60                     136  1.12     0     90   90  C    70  80  80  90   90  C                      139  1.12     20    20   40  80   30  70  70  C    90  90                     140  1.12     0     30   70  60   0   70  80  90   70  70                     141  1.12     0     20   50  70   20  80  70  70   80  90                     178  1.12     0     20   10  30   10  50  20  C    90  C                      198  1.12     0     0    0   0    0   0   0   80   20  70                     203  11.21    0     0    20  10   0   10  20  0    0   0                      205  11.21    0     0    20  0    0   0   0   10   30  10                     251  1.12     0     50   70  80   0   40  30  60   20  90                     252  1.12     0     30   60  60   20  40  30  20   10  10                     285  1.12     0     0    0   0    50  C   80  C    10  80                     287  1.12     30    0    0   0    0   70  90  C    60  80                     288  1.12     0     0    0   0    0   C   30  C    20  90                     303  11.21    0     C    C   C    C   C   C   C    C   C                      315  11.21    20    C    C   C    C   C   C   C    C   C                      329  1.12     0     0    0   0    0   70  0   C    90  C                      350  1.12     0     0    0   0    0   80  10  C    C   50                     351  1.12     0     0    0   0    0   80  80  C    C   C                      488  1.12     0     30   40  80   70  70  0   C    60  C                      500  1.21     0     10   70  80   30  60  40  70   30  90                     ______________________________________                                    

POST-EMERGENCE HERBICIDE TESTS

The post-emergence herbicidal activity of some of the various compoundsof this invention was demonstrated by greenhouse testing in thefollowing manner. Topsoil is placed in aluminum pans having holes in thebottom and compacted to a depth of 0.95 to 1.27 cm from the top of thepan. A predetermined number of seeds of each of several dicotyledonousand monocotyledonous annual plant species and/or vegetative propagulesfor the perennial plant species are placed on the soil and pressed intothe soil surface. The seeds and/or vegetative propagules are coveredwith soil and leveled. The pans are then placed on a bench in thegreenhouse and watered from below as needed. After the plants reach thedesired age (two to three weeks), each pan, is removed individually to aspraying chamber and sprayed by means of an atomizer, operating at aspray pressure of 170.3 kPa (10 psig) at the application rates noted. Inthe spray solution is an amount of an emulsifying agent mixture to givea spray solution or suspension which contains about 0.4% by volume ofthe emulsifier. The spray solution or suspension contains a sufficientamount of the candidate chemical in order to give application rates ofthe active ingredient corresponding to those shown in Tables 8 and 8A,while applying a total amount of solution or suspension equivalent to1870 L/Ha (200 gallons/acre). The pans were returned to the greenhouseand watered as before and the injury to the plants as compared to thecontrol is observed at approximately 10-14 days (usually 11 days) and insome instances observed again at 24-28 days (usually 25 days) afterspraying. The post-emergent herbicidal activity shown in these tables isthe percent inhibition of each plant species.

                  TABLE 8                                                         ______________________________________                                        POST EMERGENCE TESTS                                                          % PLANT INHIBITION                                                                                 Y   A   S   D   B   M   C   V   I                                                     W                                                                                e n e o y o o e n i                                                        Cpd.  Rate n b j b g g b l m b                                                No.  kg/ha s g g r r l u e u w                   ______________________________________                                         62          11.21   0   0   0   0   0   0   0   10  0                                                     0                                                                              63  11.21 0 20 70 20 20 C 0 C 40 C                                            64  11.21 0 20 20 0 30 60 20 60 20 80                                         65  11.21 0 0 50 10 70 50 40 70 30 70                                         66  11.21 0 0 80 30 20 70 0 50 30 C                                           67  11.21 20 20 80 40 40 70 20 80 40 C                                        68   11.21 0 0 0 0 0 0 0 0 0 0                                                69  11.21 0 0 0 0 0 10 0 10 0 0                                               70  11.21 0 10 10 10 40 40 30 50 20 N                                         71  11.21 0 0 0 0 0 20 30 20 20 40                                            72  11.21 10 10 10 20 50 30 60 90 30 90                                       73  11.21 0 0 0 0 0 0 10 20 20 20                                             74   1.12 10 0 10 10 10 20 20 40 40 90                                        75  11.21 0 0 0 0 0 10 0 0 0 60                                               76   1.12 10 40 40 30 50 50 40 90 70 C                                        77  11.21 0 20 20 0 20 10 20 30 60 60                                         78  11.21 0 0 10 10 0 10 10 40 40 30                                          79  11.21 10 60 30 20 20 60 20 C 90 C                                         80  11.21 0 0 0 0 0 10 10 60 0 N                                              81  11.21 50 0 70 10 70 60 40 80 10 90                                        82  11.21 10 0 40 20 30 90 0 20 30 60                                         83  11.21 20 0 60 40 40 80 70 C 90 C                                          84  11.21 10 10 40 0 10 50 20 C 0 N                                           85  11.21 20 60 90 50 70 C 40 C 20 C                                          86  11.21 10 30 80 0 80 C 70 C 60 C                                           87  11.21 10 10 40 0 20 70 50 C 30 40                                         88  11.21 0 10 70 10 50 C C C 60 C                                            90  11.21 0 10 0 10 0 60 30 C 50 50                                           91   1.12 10 50 40 40 30 60 C 40 50 80                                        92   1.12 20 30 40 50 30 C 80 C 80 80                                         94   1.12 10 90 90 C C 90 80 C 80 C                                           95   1.12 10 60 50 40 80 80 C C 70 C                                          96   1.12 40 C C C C C 90 C C C                                               97   1.12 50 70 60 90 C 90 C C C C                                            99  11.21 10 C C 90 C C 90 C C C                                             100   1.12 20 C C C C C 80 C 80 C                                             101   1.12 30 90 70 C C C C C C C                                             102   1.12 20 90 C C 90 C 60 C C C                                            103   1.12 10 40 70 30 80 80 60 C 70 C                                        104   1.12 20 30 80 40 50 C 70 C 40 C                                         105   1.12 20 30 20 0 20 40 20 80 30 C                                        106   1.12 10 30 40 20 60 C 60 C 60 90                                        107   1.12 10 0 20 0 30 50 50 90 40 90                                        108  11.21 0 90 90 C C C C C C C                                              109   1.12 10 40 20 0 30 60 40 C 40 90                                        110   1.12 20 30 40 20 70 80 60 C 30 C                                        111 = 11.21 30 0 20 20 60 C C C 80 C                                          112  11.21 40 30 30 0 60 80 60 C 40 70                                        113  11.21 0 0 0 0 0 30 20 50 0 20                                            114  11.21 10 10 0 0 0 50 20 50 10 60                                         115   1.12 20 40 40 20 80 60 60 C 60 C                                        116   1.12 20 80 70 70 80 C C C 80 80                                         117   1.12 20 90 C C C C 90 C 90 C                                            118   1.12 30 30 30 20 30 60 80 90 30 C                                       119  11.21 20 C C C C C C C C C                                               120   1.12 10 40 80 50 80 C 90 C 70 C                                         121  11.21 20 40 90 90 C C 90 C 90 C                                          122   1.12 20 20 70 20 70 80 60 C 50 90                                       123   1.12 20 0 50 60 50 C 70 C 30 90                                         124  11.21 20 70 C 50 90 C 70 C 90 C                                          125   1.12 0 20 0 0 0 30 40 C 30 C                                            126   1.12 10 40 30 0 50 60 30 90 40 80                                       127   1.12 20 20 C 80 60 C C C C C                                            128   1.12 20 30 C C 50 C C C 90 C                                            129   1.12 30 40 90 80 80 90 C C 90 C                                         130   1.12 20 20 70 30 40 C C C 40 C                                          131   1.12 30 20 50 20 0 C C C 40 C                                           132  11.21 30 60 C 80 C C C C C C                                             133   1.12 40 0 50 20 50 C C C 40 80                                          134   1.12 20 C C C C C C C C C                                               135   1.12 20 C C C C C C C C C                                               137   1.12 20 C C C C C C C C C                                               138   1.12 20 C C C C C C C C C                                               142   1.12 30 C C C C C C C C C                                               143   1.12 20 C 0 C C C C C C C                                               144   1.12 20 60 90 C 70 C C C C C                                            145   1.12 20 80 80 C 70 80 C C C C                                           146   1.12 30 80 80 40 90 C C C 90 C                                          147   1.12 30 0 70 0 80 C C C 40 C                                            148    1.12 20 C C C C C C C C C                                              149   1.12 20 0 40 0 30 C 70 C 50 C                                           150   1.12 20 C C C C C C C 90 C                                              151   1.12 20 C C C C C C C 80 C                                              152   1.12 20 30 20 40 0 50 40 60 50 90                                       153   1.12 10 40 90 40 30 C 40 C 50 90                                        154   1.12 20 20 70 40 80 C 80 C 40 80                                        155   1.12 20 30 80 90 80 C 40 C 50 80                                        156   1.12 10 30 70 60 30 80 50 C 70 C                                        157   1.12 20 50 80 40 60 80 50 C 70 C                                        158   1.12 20 50 80 60 50 C 80 C 20 90                                        159  11.21 50 50 C C C C C C 80 C                                             160   1.12 30 70 80 60 80 C C C 80 C                                          161  11.21 20 C C C C C C C C C                                               162   1.12 10 10 40 30 20 50 20 30 10 90                                      163  11.21 30 60 50 30 60 C 30 C 30 C                                         164  11.21 0 0 0 0 0 20 40 20 40 30                                             11.21 0 30 30 0 20 20 40 30 60 20                                           165  11.21 10 80 80 80 C 40 C 20 C                                            166   1.12 0 20 30 0 0 20 20 60 30 90                                         167  11.21 0 60 C 60 90 90 90 C C C                                             11.21 20 60 80 50 80 80 70 C 90 C                                           168  11.21 40 20 80 20 70 80 C C 60 C                                         169   1.12 30 30 80 30 50 90 70 90 50 C                                       170  11.21 20 50 80 40 70 90 70 90 70 C                                         11.21 0 40 80 20 80 90 80 C 90 C                                            171  11.21 0 10 50 30 50 20 40 C 30 C                                         172   1.12 20 0 40 20 30 50 60 80 30 30                                       173   1.12 20 0 40 20 20 70 80 70 30 60                                       174   1.12 20 40 20 30 60 70 80 30 80                                         175  11.21 20 40 90 90 90 C 60 C 60 C                                         176  11.21 20 90 90 80 90 C 90 C 90 C                                         177  11.21 10 60 C C C C C C C C                                              179   1.12 30 80 90 60 80 C 70 C 80 C                                         180   1.12 30 40 90 70 C 90 80 C C C                                          181  11.21 40 50 C 80 C 90 C C C C                                            182  11.21 20 C C C C C C C C C                                               183   1.12 0 40 80 50 60 80 80 90 50 C                                        184  11.21 30 20 60 20 70 C C C 60 C                                          185  11.21 20 30 80 30 70 90 90 C 80 C                                        186   1.12 30 80 80 90 80 C 80 C 80 C                                         187   1.12 0 40 70 30 40 40 70 80 30 90                                       188  11.21 30 80 C C 90 90 C C 80 C                                           189   1.12 30 20 60 20 40 50 40 80 40 80                                      190   1.12 20 0 50 20 30 C 90 C 50 50                                         191  11.21 10 30 C 20 60 C 40 90 90 C                                         192  11.21 30 C C C C C C C C C                                               193  11.21 0 20 70 60 80 C C C 80 90                                          194   1.12 20 50 70 30 80 90 90 C 60 90                                       195   1.12 30 30 30 40 80 90 C C 50 80                                        196   1.12 30 30 60 40 70 90 90 C 60 80                                       197  11.21 10 50 80 30 C 80 90 C 90 C                                         199   1.12 30 30 80 30 60 C 50 C 50 30                                        200   1.12 20 20 20 30 30 C 80 C 60 50                                        201   1.12 0 0 20 20 0 C 70 C 40 50                                           202   1.12 20 0 30 20 20 C 60 80 30 50                                        204   1.12 0 0 20 0 0 0 10 20 0 30                                            206  11.21 0 30 90 50 80 70 40 C 60 C                                         207   1.12 0 0 20 0 0 30 30 40 30 20                                          208   1.12 10 60 90 60 90 C 90 C C C                                          209   1.12 10 0 0 0 0 20 20 40 0 40                                           210   1.12 10 10 10 10 10 90 50 40 20 90                                      211   1.12 0 20 70 50 70 80 60 C 30 C                                         212   1.12 40 90 90 80 C 90 90 C 90 90                                        213   1.12 30 20 10 30 40 60 C 90 90 90                                       214   1.12 30 60 60 80 40 60 90 60 90 90                                      215   1.12 10 30 50 40 80 C C C C 90                                          216   1.12 10 60 C 80 80 90 60 C 60 C                                         217   1.12 20 90 90 C 90 90 90 C 90 C                                         218   1.12 30 C C C C C 90 C 90 C                                             219   1.12 60 50 C C C C C C 90 90                                            220   1.12 40 C 90 90 C C C C C C                                             221   1.12 50 90 90 C C C 90 C C C                                            222   1.12 80 0 20 90 90 90 80 C C 90                                         223   1.12 30 90 90 C C 90 C C C C                                            224   1.12 40 50 80 60 90 90 C C 80 C                                         225   1.12 30 90 90 60 C C C C 90 C                                           226   1.12 30 60 70 C C 90 C C C 90                                           227   1.12 60 90 90 C C 90 C C 90 90                                          228   1.12 80 90 C C C C C C C C                                              229   1.12 40 70 C 90 C C C C C C                                             230   1.12 40 30 50 30 90 C C C 60 90                                         231   1.12 20 0 20 20 70 50 50 90 40 80                                       232   1.12 10 C C C 90 90 C C 90 C                                            233   1.12 10 60 40 50 90 90 C 90 90 90                                       234   1.12 10 0 10 0 0 50 90 C 20 C                                           235   1.12 0 0 0 0 0 50 90 C 10 90                                            236   1.12 10 50 90 C 50 C 90 C C 90                                          237   1.12 20 40 60 60 90 90 90 C 70 90                                       238   1.12 30 20 60 20 40 80 80 90 40 C                                       239   1.12 80 90 90 C C C C C C 90                                            240   1.12 30 C C C C C C C C C                                               241   1.12 20 C 50 90 C 60 80 C 70 90                                         242   1.12 30 60 50 90 C 90 90 C C C                                          243   1.12 30 60 50 C C 90 90 C 90 C                                          244   1.12 20 20 20 0 30 50 40 50 50 50                                       245   1.12 20 30 30 90 50 90 90 C 90 90                                       246   1.12 30 C C C C C C C C C                                               247   1.12 60 40 80 C C 90 90 C C C                                           248   1.12 60 40 60 50 C 90 90 90 90 C                                        249   1.12 30 90 90 C C 80 90 C C C                                           250   1.12 10 C C C C C 90 C C 90                                             253   1.12 10 90 90 90 80 80 80 C 90 C                                        254   1.12 10 C C C C C C C C C                                               255   1.12 40 C C C C C C C C C                                               256   1.12 40 80 C 90 90 80 90 C 90 C                                         257   1.12 20 50 80 60 70 C 70 C 60 90                                        258   1.12 30 40 60 30 50 C 80 C 80 90                                        259   1.12 20 0 0 0 0 30 70 30 40 40                                          260   1.12 20 30 50 60 80 60 40 C 60 90                                       261 - 11.21 20 C C C C C C C C C                                              262   1.12 20 C C C C C C C C C                                               263   1.12 30 30 70 70 70 80 60 C 60 90                                       264   1.12 40 C C C C C C C C C                                               265   1.12 20 C C C C C 90 C 90 C                                             266   1.12 20 C C 90 C C C C 90 C                                             267   1.12 10 C C C 90 90 90 C 90 C                                           268   1.12 20 80 90 C C 90 C C 50 90                                          269   1.12 30 90 C 70 90 C 90 C 90 N                                          270   1.12 60 90 90 C C C 90 C 90 C                                           271   1.12 20 70 40 60 50 C C C 50 C                                          272   1.12 30 60 40 50 60 C C C 60 C                                          273   1.12 20 70 40 80 50 C 60 90 60 C                                        274   1.12 0 40 50 50 30 C 60 70 40 80                                        275   1.12 20 40 80 70 50 C 80 90 40 C                                        276   1.12 20 50 50 30 80 90 30 90 50 N                                       277   1.12 20 90 C 90 C C 80 C 60 C                                           278   1.12 40 C C C C C C C 90 C                                              279  11.21 50 10 C 80 C C C C C C                                             280  11.21 60 0 C 40 80 C C C C C                                             281   1.12 0 0 0 0 0 30 30 30 30 30                                              1.12 0 0 0 0 0 50 40 20 0 60                                               282   1.12 10 0 20 0 30 70 C C 10 C                                           283   1.12 0 10 50 30 40 90 C C 50 90                                         286   1.12 20 0 30 0 50 C C C 30 90                                           289   1.12 20 10 50 20 60 90 C C 40 C                                         290   1.12 20 0 40 10 50 C C C 60 C                                           291   1.12 30 0 30 20 20 C C C 40 90                                          292   1.12 10 0 0 0 40 60 80 C 20 C                                           293   1.12 20 0 20 0 60 C C C 10 C                                            294   1.12 0 20 30 20 20 80 50 50 20 30                                          1.12 0 0 0 0 0 90 80 80 0 0                                                295   1.12 30 60 80 30 50 90 70 90 80 C                                       296   1.12 20 0 10 10 10 90 90 C 30 90                                        297   1.12 10 20 20 20 0 60 60 80 20 C                                        298   1.12 20 30 30 30 20 90 C C 60 C                                         299   1.12 20 20 30 30 30 C C C 30 90                                         300   1.12 40 0 60 20 80 C C C 30 90                                          301  11.21 0 10 60 40 60 60 20 30 20 90                                       302   1.12 10 C C C C C C C C C                                               304   1.12 30 90 C 80 C 90 90 C C C                                           305   1.12 10 80 70 90 C C C C C C                                            306   1.12 40 C C C C C C C C C                                               307   1.12 20 90 C C C C 90 C 90 C                                            308   1.12 20 C C C C 90 90 C 90 C                                            309   1.12 60 C C C C C C C 90 C                                              310   1.12 30 40 40 30 60 C 80 90 60 C                                        311   1.12 40 C 80 C 90 C C C 80 C                                            312 - 11.21 10 C C C C C C C 90 C                                             313   1.12 20 C 90 C C C 70 C 60 C                                            314   1.12 30 90 90 C C C 90 C 90 C                                           316   1.12 20 30 50 40 40 50 50 60 30 C                                       317 =  1.12 20 20 70 0 70 C C C 80 C                                          318 = 11.21 40 40 C 80 90 C C C 90 C                                          319 =  1.12 20 0 0 0 0 C C C 60 C                                             320 =  1.12 20 20 80 30 70 C C C 80 C                                         321   1.12 0 0 20 20 20 30 60 C 30 C                                          322   1.12 30 70 80 50 60 60 80 90 30 C                                       323   1.12 20 50 30 20 30 80 70 90 30 C                                       324   1.12 20 C C C C 90 C C 90 90                                            325 - 11.21 10 C C C 90 C C C 90 C                                            326  11.21 20 C C C 90 C C C 50 C                                             327  11.21 0 20 0 20 50 50 30 50 10 90                                        328   1.12 0 40 50 20 60 50 80 C 30 C                                         330   1.12 10 20 60 30 90 90 90 C 60 C                                        331   1.12 30 80 C C 90 C C C 90 C                                            332   1.12 0 20 50 30 60 80 60 C 60 C                                         333   1.12 0 30 40 30 80 60 50 80 40 C                                        334   1.12 20 40 40 20 30 70 50 80 50 90                                      335   1.12 20 30 90 80 80 C C C 90 C                                          336   1.12 20 60 60 90 90 C 80 C 80 C                                         337   1.12 20 20 60 80 50 C C C 60 C                                          338   1.12 20 30 90 90 80 C C C 80 C                                          339   1.12 0 0 0 30 40 C C C 50 90                                            340   1.12 0 30 30 0 50 C C C 50 90                                           341   1.12 20 C C C C C C C 90 C                                              342   1.12 40 90 90 C C C C C 80 C                                            343  11.21 20 30 60 40 40 80 80 80 60 80                                      344   1.12 10 0 0 0 0 20 20 40 0 0                                            345   1.12 0 0 0 0 20 40 20 30 20 20                                          346  11.21 30 0 20 10 10 50 50 C 60 70                                        347  11.21 0 50 70 30 80 C 80 90 60 60                                        348   1.12 0 20 30 20 50 C 50 80 40 40                                        349   1.12 20 20 0 20 20 30 40 60 30 60                                       352  11.21 0 0 10 0 0 10 10 0 0 90                                            353  11.21 10 90 C C 90 90 80 C 90 C                                          354   1.12 10 30 40 20 0 20 10 10 30 30                                       355  11.21 10 10 40 10 60 90 40 50 40 C                                       356  11.21 20 20 90 30 80 80 40 90 30 C                                       357  11.21 0 0 10 10 10 20 10 30 10 20                                        358  11.21 10 0 10 10 20 90 30 90 90 90                                       359   1.12 0 0 0 0 0 0 10 10 0 70                                             360  11.21 0 0 0 0 0 0 0 40 20 50                                             361  11.21 10 0 0 0 10 0 10 10 0 30                                           362  11.21 10 0 0 0 0 0 10 10 0 20                                            363  11.21 0 0 30 30 20 90 30 C 30 90                                         364  11.21 0 0 0 10 0 20 10 10 10 40                                          365  11.21 0 30 80 30 30 70 30 90 20 C                                        366 - 11.21 10 30 60 60 80 C 40 C 60 C                                        367  11.21 0 0 0 10 10 30 20 20 10 N                                          368  11.21 0 0 0 0 0 0 10 10 10 N                                             369  11.21 0 20 0 0 30 20 20 20 40 90                                         370  11.21 0 10 10 10 40 20 20 30 30 C                                        371  11.21 0 0 0 0 0 0 0 0 0 0                                                372  11.21 0 0 0 0 20 30 20 20 20 60                                          373  11.21 0 10 10 10 80 20 50 50 50 90                                       374  11.21 0 10 40 10 40 90 20 60 80 C                                        375  11.21 0 0 10 0 10 20 10 10 20 30                                         376  11.21 0 C 60 50 50 60 80 90 90 90                                        377  11.21 20 90 30 90 60 90 90 90 90 90                                      378  11.21 0 0 0 0 10 40 20 20 90 90                                          379  11.21 0 0 10 10 30 40 20 20 90 90                                        380  11.21 0 0 30 20 20 40 30 50 30 70                                        381   1.12 0 0 0 0 0 20 20 0 20 0                                             382  11.21 0 0 20 0 30 30 30 60 50 90                                         383  11.21 0 0 20 0 0 30 20 40 20 10                                          384  11.21 0 0 0 0 0 0 20 30 20 50                                            385  11.21 0 30 0 0 20 40 30 40 50 40                                         386  11.21 0 0 0 0 0 80 60 50 50 50                                           387  11.21 0 0 0 0 30 10 10 30 30 50                                          388  11.21 0 0 0 0 30 10 10 N 10 20                                           389 - 11.21 10 90 90 80 90 C 50 C C C                                         390 - 11.21 10 C C C 90 C 60 C 90 C                                           391   1.12 20 30 30 10 60 90 20 30 20 C                                       392   1.12 10 40 60 40 90 C 40 80 40 C                                        393   1.12 20 0 20 10 20 C 90 C 0 N                                           394   1.12 10 80 90 40 90 80 30 C 60 C                                        395   1.12 10 20 60 30 40 50 20 60 30 C                                       396  11.21 10 30 30 20 20 C 20 90 40 C                                        397   1.12 0 20 60 10 70 40 20 40 30 80                                       398   1.12 0 0 0 0 0 0 0 0 0 0                                                399   1.12 30 50 40 60 70 50 70 90 60 90                                      400  11.21 30 0 20 0 30 90 30 C 90 C                                          401   1.12 10 40 40 30 50 60 30 90 30 C                                       402   1.12 0 20 20 20 20 80 50 90 30 C                                        403  11.21 30 50 C 90 C C 90 C C C                                            404  11.21 10 60 90 90 C C 90 C 90 C                                          405  11.21 20 20 50 30 C C 90 90 C C                                          406  11.21 10 0 30 10 20 30 30 C 40 90                                        407  11.21 40 20 C C 90 C C C C C                                             408  11.21 20 40 70 30 60 50 50 C 80 C                                          11.21 0 40 40 0 40 40 80 C 80 C                                             409  11.21 0 0 30 0 40 60 90 70 30 70                                           11.21 0 40 70 20 40 70 80 70 60 80                                          410  11.21 0 0 80 60 0 50 60 90 60 C                                          411   1.12 0 0 50 0 50 60 20 90 30 C                                             1.12 30 40 80 50 80 80 40 C 60 C                                           412   1.12 0 0 20 20 20 40 30 50 20 50                                        413  11.21 0 20 50 30 70 80 60 C 40 C                                         414  11.21 10 C C C 90 C 40 C C C                                             415   1.12 30 50 30 30 80 50 40 90 30 C                                       416   1.12 20 40 60 30 30 50 50 80 40 60                                      417   1.12 20 20 50 30 40 60 60 90 50 80                                      418   1.12 0 0 0 20 30 30 0 60 0 70                                              1.12 0 0 20 20 20 40 30 30 30 60                                           419   1.12 0 20 70 0 50 50 50 C 40 C                                          420   1.12 0 10 0 0 40 50 40 60 60 90                                         421  11.21 30 80 C C C C C C C C                                              422  11.21 0 50 90 60 80 70 70 C 80 C                                         423  11.21 0 0 0 0 0 30 40 30 20 90                                           424  11.21 0 0 20 0 10 10 40 90 20 90                                         425  11.21 0 0 0 0 0 40 40 80 60 60                                             11.21 0 0 0 0 0 50 50 60 50 50                                              426 = 11.21 0 0 0 0 0 40 30 30 20 40                                          427  11.21 0 0 0 0 0 0 10 0 0 0                                               428  11.21 0 0 0 20 20 90 40 80 60 60                                         429  11.21 40 20 50 0 40 20 20 90 C 60                                        430  11.21 0 30 60 20 30 50 50 90 30 80                                       431  11.21 0 0 0 0 0 10 20 10 20 10                                           432  11.21 0 20 C 10 20 40 20 60 C C                                          433  11.21 0 0 0 0 0 0 0 0 0 0                                                435  11.21 0 40 80 20 60 80 60 C 0 C                                          436  11.21 0 0 50 0 0 20 30 20 40 0                                           437  11.21 0 0 30 0 0 60 30 40 30 50                                            11.21 0 0 20 0 0 40 20 30 0 50                                              438   1.12 30 50 40 20 30 70 60 80 30 90                                      439   1.12 20 0 50 20 30 40 60 80 30 80                                       440  11.21 20 60 60 30 50 90 70 C 70 C                                        441   1.12 10 30 40 20 30 80 80 80 40 80                                      442  11.21 0 30 50 20 50 90 50 C 70 C                                         443   1.12 20 C C C C C C C 90 C                                              444   1.12 40 0 60 0 20 80 80 C 30 30                                         445   1.12 40 C C C C C C C 90 C                                              446   1.12 40 C 90 C C C C C C C                                              447   1.12 20 40 30 60 80 C C C 90 70                                         448   1.12 20 30 40 20 50 90 70 80 20 40                                      449   1.12 10 30 50 40 60 C 80 C 10 40                                        450   1.12 10 40 40 30 40 C 80 C 20 50                                        451   1.12 20 0 0 0 20 40 40 50 20 50                                         452   1.12 10 20 40 0 40 C 80 70 60 90                                        453   1.12 20 40 40 20 50 C C 80 30 90                                        454   1.12 30 C C C C C C C 90 80                                             455   1.12 20 C C C C C 80 C C 90                                             456   1.12 50 C 90 C 80 C C C 70 90                                           457   1.12 10 70 90 C C C 90 C C 60                                           458   1.12 20 C C C C C 80 C C C                                              459   1.12 20 C C C C C C C C C                                               460    1.12 20 C C C C C 80 C C C                                             461   1.12 20 C C C C C C C C C                                               462  11.21 0 30 50 20 10 40 30 C 40 90                                        463   1.12 40 30 60 90 C 90 C C C 90                                          464   1.12 20 C C C C C C C C C                                               465  11.21 50 C C C C C C C C C                                               466  11.21 40 40 80 50 70 C C C C C                                           467  11.21 40 80 80 40 90 C 80 C C C                                          468   1.12 30 C C C C 90 C C C C                                              469   1.12 20 10 30 20 80 80 80 C 60 90                                       470   1.12 0 0 0 0 0 20 20 0 0 0                                              471  11.21 40 90 C 70 C C C C C C                                             472  11.21 10 20 50 20 30 60 50 C C 70                                        473  11.21 0 0 0 10 0 60 30 50 30 50                                          474  11.21 20 80 C 90 C C C C C C                                             475  11.21 10 20 70 0 60 C 30 C C 90                                          476  11.21 0 0 0 0 0 0 0 0 0 0                                                477  11.21 0 0 0 0 0 0 0 0 0 0                                                478  11.21 0 20 20 20 20 70 70 90 40 80                                       479  11.21 0 0 0 0 0 10 10 0 0 0                                              480  11.21 0 0 0 0 0 30 0 20 50 0                                             481  11.21 10 50 90 40 50 90 40 C 40 90                                       482  11.21 20 C C C C 90 C C C C                                              484   5.61 0 0 0 0 30 50 20 60 50 80                                          485  11.21 0 0 20 0 20 60 60 80 30 90                                         486   1.12 30 30 10 20 40 80 70 40 40 80                                      487  11.21 0 0 0 0 0 20 30 70 20 80                                           489  11.21 10 10 10 0 0 20 20 90 0 30                                          =  1.12 0 0 0 0 0 20 0 0 20 0                                                490   1.12 20 60 C 90 C C 70 C 80 C                                           491  11.21 0 0 30 0 40 50 50 60 30 70                                         492  11.21 0 0 0 30 0 10 0 0 0 0                                              493  11.21 0 0 20 0 50 40 40 50 20 60                                           11.21 0 0 0 0 30 0 0 20 20 40                                               494  11.21 0 0 0 0 0 20 20 20 0 10                                            495   1.12 0 0 0 0 20 20 20 40 50 50                                          496   1.12 0 0 0 0 0 0 10 10 30 0                                             497  11.21 0 0 0 0 0 0 0 0 20 40                                              498  11.21 0 0 0 0 0 80 50 90 30 90                                           499  11.21 10 0 10 0 30 20 20 20 20 40                                        501  11.21 0 50 60 30 30 80 30 80 30 50                                          1.12 0 0 0 0 0 0 0 0 0 0                      ______________________________________                                          Wibw was generally thin.                                                     = Cobu germination was erratic                                                - VOLATILE.                                                                   TEST CONTAMINATION DUE TO VOLATILE COMPOUNDS.                            

                  TABLE 8A                                                        ______________________________________                                        POST EMERGENCE TESTS                                                          % PLANT INHIBITION                                                                          Y     A    S   D    B   M   C   V    I   W                                    e     n    e   o    y   o   o   e    n   i                      Cpd. Rate     n     b    j   b    g   g   b   l    m   b                      No.  kg/ha    s     g    g   r    r   l   u   e    u   w                      ______________________________________                                         89  11.21    0     10   70  10   20  C   C   C    80  80                      93  1.12     0     10   40  50   70  60  70  90   60  90                      98  1.12     0     70   90  90   80  C   C   C    80  80                     136  1.12     10    C    C   C    C   C   C   C    C   C                      139  1.12     10    90   C   C    C   C   90  C    C   C                      140  1.12     10    C    C   C    C   C   C   C    90  90                     141  1.12     0     90   90  C    70  C   90  C    80  C                      178  1.12     0     90   70  90   70  C   90  C    70  C                      198  1.12     0     50   70  70   50  90  70  C    C   C                      203  11.21    0     20   60  30   50  60  60  C    60  90                     205  11.21    0     40   70  50   10  80  60  C    60  90                     251  1.12     10    80   C   C    90  C   90  C    70  90                     252  1.12     20    90   C   C    90  C   C   C    C   C                      285  1.12     40    30   50  40   70  C   C   C    C   C                      287  1.12     10    0    80  10   70  C   C   C    20  90                     288  1.12     10    0    20  0    50  C   C   C    90  C                      303  11.21    70    C    C   C    C   C   C   C    C   C                      315  11.21    20    C    C   C    C   C   C   C    C   C                      329  1.12     0     90   90  90   90  C   90  C    C   C                      350  1.12     30    20   70  0    60  90  C   C    C   C                      351  1.12     30    30   60  40   70  C   C   C    C   C                      488  1.12     0     90   C   90   90  C   C   C    C   C                      500  11.21    --    --   --  0    0   0   0   0    0   0                           11.21    0     50   90  70   90  C   C   C    90  C                      ______________________________________                                    

The herbicidal compositions of this invention, including concentrateswhich require dilution prior to application, may contain at least oneactive ingredient and an adjuvant in liquid or solid form. Thecompositions are prepared by admixing the active ingredient with anadjuvant including diluents, extenders, carriers, and conditioningagents to provide compositions in the form of finely-divided particulatesolids, granules, pellets, solutions, dispersions or emulsions. Thus, itis believed that the active ingredient could be used with an adjuvantsuch as a finely-divided solid, a liquid of organic origin, water, awetting agent, a dispersing agent, an emulsifying agent or any suitablecombination of these.

Suitable wetting agents are believed to include alkyl benzene and alkylnaphthalene sulfonates, sulfated fatty alcohols, amines or acid amides,long chain acid esters of sodium isothionate, esters of sodiumsulfosuccinate, sulfated or sulfonated fatty acid esters, petroleumsulfonates, sulfonated vegetable oils, ditertiary acetylenic glycols,polyoxyethylene derivatives of alkylphenols (particularly isooctylphenoland nonylphenol) and polyoxyethylene derivatives of the mono-higherfatty acid esters of hexitol anhydrides (e.g., sorbitan). Preferreddispersants are methyl cellulose, polyvinyl alcohol, sodium ligninsulfonates, polymeric alkyl naphthalene sulfonates, sodium naphthalenesulfonate, and polymethylene bisnaphthalene sulfonate. Wettable powdersare water-dispersible compositions containing one or more activeingredients, an inert solid extender and one or more wetting anddispersing agents. The inert solid extenders are usually of mineralorigin such as the natural clays, diatomaceous earth and syntheticminerals derived from silica and the like. Examples of such extendersinclude kaolinites, attapulgite clay and synthetic magnesium silicate.The wettable powders compositions of this invention usually contain fromabove 0.5 to 60 parts (preferably from 5-20 parts) of active ingredient,from about 0.25 to 25 parts (preferably 1-15 parts) of wetting agent,from about 0.25 to 25 parts (preferably 1.0-15 parts) of dispersant andfrom 5 to about 95 parts (preferably 5-50 parts).of inert solidextender, all parts being by weight of the total composition. Whererequired, from about 0.1 to 2.0 parts of the solid inert extender can bereplaced by a corrosion inhibitor or anti-foaming agent or both.

Other formulations include dust concentrates comprising from 0.1 to 60%by weight of the active ingredient on a suitable extender; these dustsmay be diluted for application at concentrations within the range offrom about 0.1-10% by weight.

Aqueous suspensions or emulsions may be prepared by stirring anonaqueous solution of a water-insoluble active ingredient and anemulsification agent with water until uniform and then homogenizing togive stable emulsion of very finely divided particles. The resultingconcentrated aqueous suspension is characterized by its extremely smallparticle size, so that when diluted and sprayed, coverage is veryuniform. Suitable concentrations of these formulations contain fromabout 0.1-60%, preferably 5-50% by weight of active ingredient, theupper limit being determined by the solubility limit of activeingredient in the solvent. Concentrates are usually solutions of activeingredient in water-immiscible or partially water-immiscible solventstogether with a surface active agent. Suitable solvents for the activeingredient of this invention include dimethylformamide,dimethylsulfoxide, N-methylpyrrolidone, hydrocarbons, andwater-immiscible ethers, esters, or ketones. However, other highstrength liquid concentrates may be formulated by dissolving the activeingredient in a solvent then diluting, e.g., with kerosene, to sprayconcentration.

The concentrate compositions herein generally contain from about 0.1 to95 parts (preferably 5-60 parts) active ingredient, about 0.25 to 50parts (preferably 1-25 parts) surface active agent and where requiredabout 5 to 94 parts solvent, all parts being be weight based on thetotal weight of emulsifiable oil.

Granules are physically stable particulate compositions comprisingactive ingredient adhering to or distributed through a basic matrix ofan inert, finely-divided particulate extender. In order to aid leachingof the active ingredient from the particulate extender, a surface activeagent can be present in the composition. Natural clays, pyrophyllites,illite, and vermiculite are examples of operable classes of particulatemineral extenders. The preferred extenders are the porous, absorptive,preformed particles such as preformed and screened particulateattapulgite or heat expanded, particulate vermiculite and thefinely-divided clays such as kaolin clays, hydrated attapulgite orbentonitic clays. These extenders are sprayed or blended with the activeingredient to form the herbicidal granules.

The granular compositions of this invention may contain from about 0.1to about 30 parts by weight of active ingredient per 100 parts by weightof clay and 0 to about 5 parts by weight of surface active agent per 100parts by weight of particulate clay

The compositions of this invention can also contain other additaments,for example, fertilizers, other herbicides, other pesticides, safenersand the like used as adjuvants or in combination with any of theabove-described adjuvants. Chemicals useful in combination with theactive ingredients of this invention included, for example, triazines,ureas, sulfonylureas, carbamates, acetamides, acetanilides, uracils,acetic acid or phenol derivatives, thiolcarbamates, triazoles,azolopyrimidines, benzoic acid and its derivatives, nitriles, biphenylethers, nitrobenzenes and the like such as:

Heterocyclic Nitrogen/Sulfur Derivatives

2-Chloro-4-ethylamino-6-isopropylamino-s-triazine

2-Chloro-4,6-bis(isopropylamino)-s-triazine

2-Chloro-4,6-bis(ethylamino)-s-triazine

3-Isopropyl-1H-2,1,3-benzothiadiazin-4-(3H)-one 2,2-dioxide

3-Amino-1,2,4-triazole

6,7-Dihydrodipyrido(1,2-:2', 1'-c)-pyrazidiinium salt

5-Bromo-3-isopropyl-6-methyluracil

1,1,'-Dimethyl-4,4'-bypyridinium

2-(4-Isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-3-quinolinecarboxylicacid

Isopropylamine salt of2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid

Methyl 6-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-m-toluate andmethyl 2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-p-toluate

Ureas/Sulfonylureas

N-(4-Chlorophenoxy) phenyl-N,N-dimethylurea

N,N-dimethyl-N'-(3-chloro-4-methylphenyl) urea

3-(3,4-dichlorophenyl)-1,1-dimethylurea

1,3-Dimethyl-3-(2-benzothiazolyl) urea

3-(p-Chlorophenyl)-1,1-dimethylurea

1-Butyl-3-(3,4-dichlorophenyl)-1-methylurea

2-Chloro-N[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-benzenesulfonamide

N-(2-methoxycarbonylphenylsulfonyl()-N'-(4,6-bis-difluoromethoxypyrimidin-2-yl)urea

Methyl 2-(((((4,6-dimethyl-2-pyrimidinyl)amino)carbonyl)amino)sulfonyl)benzoate

Ethyl 1-[methyl2-(((((4,6-dimethyl-2-pyrimidinyl)amino)carbonyl)amino)sulfonyl)]benzoate

Methyl-2((4,6-dimethoxy pyrimidin-2-yl)aminocarbonyl)amino sulfonylmethyl) benzoate

Methyl2-(((((4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino)carbonyl)amino)sulfonyl)benzoate

Carbamates/Thiolcarbamates

2-Chloroallyl diethyldithiocarbamate

S-(4-chlorobenzyl)N,N-diethylthiolcarbamate

Isopropyl N-(3-chlorophenyl) carbamate

S-2,3-dichloroallyl N,N-diisopropylthiolcarbamate

S-N,N-dipropylthiolcarbamate

S-propyl N,N-dipropylthiolcarbamate

S-2,3,3-trichloroallyl-N,N-diisopropylthiolcarbamate

Acetamides/Acetanilides/Anilines/Amides

2-Chloro-N, N-diallylacetamide

N,N-dimethyl-2,2-diphenylacetamide

N-(2,4-dimethylthien-3-yl)-N-(1-methoxyprop-2-yl)-2-chloroacetamide

N-(1H-pyrazol-1-ylmethyl-N-(2,4-dimethylthien-3-yl)-2-chloroacetamide

N-(1-pyrazol-1-ylmethyl)-N-(4,6-dimethoxypyrimidin-5-yl)-2-chloroacetamide

N-(2,4-dimethyl-5-[[[(trifluoromethyl)sulfonyl]amino]-phenyl]acetamide

N-Isopropyl-2-chloroacetanilide

N-Isopropyl-1-(3,5,5-trimethylcyclohexen-1-yl)-2-chloroacetamide

2',6'-Diethyl-N-(butoxymethyl)-2-chloroacetanilide

2',6'-Diethyl-N-(2-n-propoxyethyl)-2-chloroacetanilide

2',6'-Dimethyl-N-(1-pyrazol-1-ylmethyl)-2-chloroacetanilide

2',6'-Diethyl-N-methoxymethyl-2-chloroacetanilide

2'-Methyl-6'-ethyl-N-(2-methoxyprop-2-yl)-2-chloroacetanilide

2'-Methyl-6'-ethyl-N-(ethoxymethyl)-2-chloroacetanilide

α,α,α-Trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine

N-(1,1-dimethylpropynyl)-3,5-dichlorobenzamide

Acids/Esters/Alcohols

2,2-Dichloropropionic acid

2-Methyl-4-chlorophenoxyacetic acid

2,4-Dichlorophenoxyacetic acid

Methyl-2-[4-(2,4-dichlorophenoxy)phenoxy]propionate

3-Amino-2,5-dichlorobenzoic acid

2-Methoxy-3,6-dichlorobenzoic acid

2,3,6-Trichlorophenylacetic acid

N-1-naphthylphthalamic acid

Sodium 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate

4,6-Dinitro-o-sec-butylphenol

N-(phosphonomethyl)glycine and its salts

Butyl (R)-2-[4-[(5-(trifluoromethyl)-2-pyridinyl)oxy]phenoxy]propanoate

Ethers

2,4-Dichlorophenol-4-nitrophenyl ether

2-Chloro-δ,δ,δ-trifluoro-p-tolyl-3-ethoxy-4-nitrodiphenyl ether

5-(2-chloro-4-trifluoromethylphenoxy)-N-methylsulfonyl 2-nitrobenzamide

1'-(Carboethoxy) ethyl5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate

Miscellaneous

2,6-Dichlorobenzonitrile

Monosodium acid methanearsonate

Disodium methanearsonate

2-(2-chlorophenyl)methyl-4,4-dimethyl-3-isoxazolidinone

7-Oxabicyclo (2.2.1) heptane,1-methyl-4-(1-methylethyl)-2-(2-methylphenylmethoxy)-, exoGlyphosate andsalts thereof.

Fertilizers useful in combination with the active ingredients include,for example, ammonium nitrate, urea, potash and superphosphate. Otheruseful additaments include materials in which plant organisms take rootand grow such as compost, manure, humus, sand and the like.

Herbicidal formulations of the types described above contemplated aswithin the purview of this invention are exemplified in severalillustrative embodiments below.

    ______________________________________                                                               Weight Percent                                         ______________________________________                                        I. Emulsifiable Concentrates                                                  A.  Compound No. 308         11.0                                                 Free acid of complex organic phosphate                                                                 5.59                                                 or aromatic or aliphatic hydrophobe                                           base (e.g., GAFAC RE-610, registered                                          trademark of GAF Corp.)                                                       Polyoxyethylene/polyoxypropylene block                                                                 1.11                                                 copolymer with butanol (e.g., Tergitol XH,                                    registered trademark of Union Carbide                                         Corp.)                                                                        Phenol                   5.34                                                 Monochlorobenzene        76.96                                                                         100.00                                           B.  Compound No. 261         25.00                                                Free acid of complex organic phosphate                                                                 5.00                                                 of aromatic or aliphatic hydrophobe                                           base (e.g., GAFAC RE-610)                                                     Polyoxyethylene/polyoxypropylene block                                                                 1.60                                                 copolymer with butanol (e.g., Tergitol                                        XH)                                                                           Cyclohexanone            4.75                                                 Monochlorobenzene        63.65                                                                         100.00                                           C.  Compound No. 291         12.0                                                 Free acid of complex organic phosphate                                                                 6.0                                                  or aromatic or aliphatic hydrophobe                                           base (e.g., GAFAC RE-610, registered                                          trademark of GAF Corp.)                                                       Polyoxyethylene/polyoxypropylene block                                                                 1.5                                                  copolymer with butanol (e.g., Tergitol XH,                                    registered trademark of Union Carbide                                         Corp.)                                                                        Cyclohexanone            5.5                                                  Monochlorobenzene        75.0                                                                          100.00                                           D.  Compound of No. 229      20.0                                                 Free acid of complex organic phosphate                                                                 5.00                                                 of aromatic of aliphatic hydrophobe                                           base (e,.g., GAFAC RE-610                                                     Polyoxyethylene/polyoxypropylene block                                                                 2.0                                                  copolymer with butanol (e.g., Tergitol                                        XH)                                                                           Cyclohexanone            5.0                                                  Monochlorobenzene        68.0                                                                          100.00                                           E.  Compound No. 312         11.0                                                 Free acid of complex organic phosphate                                                                 5.59                                                 or aromatic or aliphatic hydrophobe                                           base (e.g. GAFAC RE-610, registered                                           trademark of GAF Corp.)                                                       Polyoxyethylene/polyoxypropylene block                                                                 1.11                                                 copolymer with butanol (e.g., Tergitol XH,                                    registered trademark of Union Carbide                                         Corp.)                                                                        Cyclohexanone            5.34                                                 Monochlorobenzene        76.96                                                                         100.00                                           F.  Compound No. 282         25.00                                                Free acid of complex organic phosphate                                                                 5.00                                                 of aromatic or aliphatic hydrophobe                                           base (e.g., GAFAC RE-610                                                      Polyoxyethylene/polyoxypropylene block                                                                 1.60                                                 copolymer with butanol (e.g., Tergitol                                        XH)                                                                           Cyclohexanone            4.75                                                 Monochlorobenzene        63.65                                                                         100.00                                           II. Flowables                                                                 A.  Compound No. 261         25.0                                                 Methyl cellulose-        0.3                                                  Silica Aerogel           1.5                                                  Sodium lignosulfonate    3.5                                                  Sodium N-methyl-N-oleyl taurate                                                                        1.0                                                  Water                    67.7                                                                          100.00                                           B.  Compound No. 270         45.0                                                 Methyl cellulose         .3                                                   Silica aerogel           1.5                                                  Sodium lignosulfonate    3.5                                                  Sodium N-methyl-N-oleyl taurate                                                                        1.0                                                  Water                    47.7                                                                          100.00                                           C.  Compound No. 294         30.0                                                 Methyl cellulose         0.3                                                  Silica Aerogel           1.5                                                  Sodium lignosulfonate    3.5                                                  Sodium N-methyl-N-oleyl taurate                                                                        3.0                                                  Water                    62.0                                                                          100.00                                           D.  Compound No. 135         23.0                                                 Methyl cellulose         0.5                                                  Silica Aerogel           2.0                                                  Sodium lignosulfonate    3.5                                                  Sodium N-methyl-N-oleyl taurate                                                                        2.0                                                  Water                    69.0                                                                          100.00                                           E.  Compound No. 148         45.0                                                 Methyl cellulose         .3                                                   Silica aerogel           1.5                                                  Sodium lignosulfonate    3.5                                                  Sodium N-methyl-N-oleyl taurate                                                                        1.0                                                  Water                    47.7                                                                          100.00                                           III. Wettable Powders                                                         A.  Compound No. 261         25.0                                                 Sodium lignosulfonate    3.0                                                  Sodium N-methyl-N-oleyl-taurate                                                                        1.0                                                  Amorphous silica (synthetic)                                                                           71.0                                                                          100.0                                            B.  Compound No. 312         45.0                                                 Sodium dioctyl sulfosuccinate                                                                          1.25                                                 Calcium lignosulfonate   1.75                                                 Amorphous silica (synthetic)                                                                           52.0                                                                          100.0                                            C.  Compound No. 237         10.0                                                 Sodium lignosulfonate    3.0                                                  Sodium N-methyl-N-oleyl-taurate                                                                        1.0                                                  Kaolinite clay           86.0                                                                          100.00                                           D.  Compound No. 463         30.0                                                 Sodium lignosulfonate    3.0                                                  Sodium N-methyl-N-oleyl-taurate                                                                        1.0                                                  Kaolin                   56.0                                                 Amorphous silica (synthetic)                                                                           10.0                                                                          100.0                                            E.  Compound No. 446         75.0                                                 Sodium dioctyl sulfosuccinate                                                                          1.25                                                 Calcium lignosulfonate   1.75                                                 Kaolin                   12.0                                                 Amorphous silica synthetic                                                                             10.0                                                                          100.00                                           F.  Compound No. 482         15.0                                                 Sodium lignosulfonate    3.0                                                  Sodium N-methyl-N-oleyl-taurate                                                                        1.0                                                  Amorphous silica, synthetic                                                                            10.0                                                 Kaolinite clay           71.0                                                                          100.00                                           IV. Granules                                                                  A.  Compound No. 74          15.0                                                 Dipropylene Glycol       5.0                                                  Granular attapulgite (20/40 mesh)                                                                      80.0                                                                          100.0                                            B.  Compound No. 390         15.0                                                 Dipropylene Glycol       5.0                                                  Diatomaceous earth (20/40)                                                                             80.0                                                                          100.0                                            C.  Compound No. 399         1.0                                                  Ethylene glycol          5.0                                                  Methylene blue           0.1                                                  Pyrophyllite             93.9                                                                          100.0                                            D.  Compound No. 393         5.0                                                  Ethylene Glycol          5.0                                                  Pyrophyllite (20/40)     90.0                                                                          100.0                                            E.  Compound No. 312         15.0                                                 Propylene Glycol         5.0                                                  Granular attapulgite (20/40 mesh)                                                                      80.0                                                                          100.0                                            F.  Compound No. 324         25.0                                                 Diatomaceous earth (20/40)                                                                             75.0                                                                          100.0                                            G.  Compound No. 261         5.0                                                  Ethylene glycol          5.0                                                  Methylene blue           0.5                                                  Pyrophyllite             94.5                                                                          100.00                                           H.  Compound No. 262         10.0                                                 Propylene Glycol         5.0                                                  Pyrophyllite (20/40)     85.0                                                                          100.0                                            V. Suspension Concentrates                                                    A.  Compound No. 262         16.0                                                 Nonylphenol ethoxylate 9.5 mole                                                                        13.8                                                 EO Sterox NJ                                                                  Sodium lignosulfonate (Reax 88B)                                                                       12.2                                                 Water                    58.0                                                                          100.0                                            B.  Compound No. 446         32.5                                                 Potassium salt of napthalene sulfonate                                                                 9.0                                                  formaldehyde condensate                                                       (DAXAD 11 KLS)                                                                Nonylphenol ethoxylate 10 mole EO                                                                      9.0                                                  (Igepal CO-660)                                                               Water                    49.5                                                                          100.0                                            C.  Compound No. 76          10.0                                                 Sodium dioctyl sulfosuccinate Aerosol                                                                  11.0                                                 OTB                                                                           Castor oil + 36 Ethylene oxide                                                                         11.0                                                 (FloMo 3G)                                                                    Water                    70.0                                                                          100.0                                            D.  Compound No. 261         15.0                                                 Nonylphenol ethoxylate 9.5 mole                                                                        1.0                                                  EO Sterox NJ                                                                  Sodium lignosulfonate (Reax 88B)                                                                       5.0                                                  Water                    79.0                                                                          100.0                                            E.  Compound No. 290         30.0                                                 Potassium salt of napthalene sulfonate                                                                 4.0                                                  formaldehyde condensate                                                       (DAXAD 11 KLS)                                                                Nonylphenol ethoxylate 10 mole EO                                                                      2.0                                                  (Igepal CO-660)                                                               Water                    64.0                                                                          100.0                                            F.  Compound No. 135         18.0                                                 Nonylphenol ethoxylate 9.5 mole                                                                        14.0                                                 EO Sterox NJ                                                                  Sodium lignosultonate (Reax 88B)                                                                       12.0                                                 Water                    56.0                                                                          100.0                                            G.  Compound No. 148         34.0                                                 Potassium salt of napthalene sulfonate                                                                 8.0                                                  formaldehyde condensate (DAXAD aag)                                           Nonylphenol ethoxylate 10 mole EO                                                                      10.0                                                 (Igepal CO-660)                                                               Water                    48.0                                                                          100.0                                            H.  Compound No. 482         14.0                                                 Sodium dioctyl sulfosuccinate Aerosol                                                                  3.0                                                  OTB                                                                           Castor oil + 36 Ethylene oxide                                                                         3.0                                                  (FloMo 3G)                                                                    Water                    80.0                                                                          100.0                                            VI. Liquid Concentrates                                                       A.  Compound No. 76          20.0                                                 Xylene                   80.0                                                                          100.0                                            B.  Compound No. 229         10.0                                                 Xylene                   90.0                                                                          100.0                                            C.  Compound No. 217         25.0                                                 Xylene                   75.0                                                                          100.0                                            D.  Compound No. 482         15.0                                                 Xylene                   85.0                                                                          100.0                                            VII. Microcapsules                                                            A.  Compound No. 135 encapsulated in a                                                                     4.5                                                  polyurea shell wall                                                           Reax ™ C-21           1.5                                                  NaCl                     5.0                                                  Water                    89.0                                                                          100.0                                            B.  Compound No. 137 encapsulated in a                                                                     20.0                                                 polyurea shell wall                                                           Reax ™ 88B            2.0                                                  NaNO.sub.3               10.0                                                 Xylene                   30.0                                                 Water                    38.0                                                                          100.0                                            C.  Compound No. 138 encapsulated in a                                                                     4.8                                                  polyurea shell wall                                                           Reax ™ 88B            1.2                                                  NaNO.sub.3               5.0                                                  Kerosene                 20.0                                                 Water                    69.0                                                                          100.0                                            D.  Compound No. 148 encapsulated in a                                                                     50.0                                                 urea-formaldehyde polymer shell                                               wall                                                                          Reax ™ C-21           1.5                                                  NaCl                     8.5                                                  Petroleum oil (Aromatic 200)                                                                           20.0                                                 Water                    20.0                                                                          100.0                                            E.  Compound No. 229 encapsulated in a                                                                     30.0                                                 thiourea-formaldehyde shell                                                   wall                                                                          Reax ™ C-21           2.0                                                  NaCl                     8.0                                                  Xylene                   30.0                                                 Water                    30.0                                                                          100.0                                            F.  Compound No. 261 encapsulated in a                                                                     7.5                                                  polyurea shell wall                                                           Reax ™ 88B            1.5                                                  NaCl                     8.0                                                  Aromatic 200             30.0                                                 Water                    53.0                                                                          100.0                                            G.  Compound No. 308 encapsulated in a                                                                     9.0                                                  melamine-formaldehyde co-                                                     polymeric shell wall                                                          Reax ™ 88B            2.0                                                  NaNO.sub.3               10.0                                                 Kerosene                 40.0                                                 Water                    39.0                                                                          100.0                                            H.  Compound No. 446 encapsulated in a                                                                     15.0                                                 urea-formaldehyde polymeric                                                   shell wall                                                                    Reax ™ 88B            10.0                                                 NaNO.sub.3               8.0                                                  Xylene                   42.0                                                 Water                    25.0                                                                          100.0                                            I.  Compound No. 312 encapsulated in a                                                                     22.0                                                 polyurea shell wall                                                           Reax ™ 88B            2.0                                                  NaCl                     8.0                                                  Xylene                   35.0                                                 Water                    33.0                                                                          100.0                                            ______________________________________                                    

When operating in accordance with the present invention, effectiveamounts of the compounds of this invention are applied to the soilcontaining the seeds, or vegetative propagules or may be incorporatedinto the soil media in any convenient fashion. The application of liquidand particulate solid compositions to the soil can be carried out byconventional methods, e.g., power duster, boom and hand sprayers andspray dusters. The compositions can also be applied from airplanes as adust or a spray because of their effectiveness at low dosages. The exactamount of active ingredient to be employed is dependent upon variousfactors, including the plant species and stage of development thereof,the type and condition of soil, the amount of rainfall and the specificcompounds employed. In elective pre-emergence application or to thesoil, a dosage of from about 0.02 to about 11.2 kg/ha, preferably fromabout 0.1 to about 5.60 kg/ha, is usually employed. Lower or higherrates may be required in some instances. One skilled in the art canreadily determine from this specification, including the above examples,the optimum rate to be applied in any particular case.

The term "soil" is employed in its broadest sense to be inclusive of allconventional "soils" as defined in Webster's New InternationalDictionary, Second Edition, Unabridged (1961). Thus, the term refers toany substance or medium in which vegetation may take root and grow, andincludes not only earth but also compost, manure, muck, humus, loam,silt, mire, clay, sand and the like, adapted to support plant growth.

Although this invention has been described with respect to specificembodiments, the details of these embodiments are not to be construed aslimitations. Various equivalents, changes and modifications may be madewithout departing from the spirit and scope of this invention, and it isunderstood that such equivalent embodiments are part of this invention.

We claim:
 1. Compounds according to Formula I: ##STR95## and agriculturally acceptable salts and hydrates thereof wherein R₁ is independently C₁₋₈ alkyl; C₃₋₈ cycloalkyl, cycloalkenyl, cycloalkylalkyl, or cycloalkenylalkyl; C₂₋₈ alkenyl or alkynyl; or benzyl; or said R₁ members substituted with halogen, amino, nitro, cyano, hydroxy, alkoxy, alkylthio, ##STR96## YR₁₀, or NR₁₁ R₁₂ ; R₂ is C₁₋₅ haloalkyl;R₃ is halogen; R₄ is an R₁ member, alkylthio, alkoxyalkyl or polyalkoxyalkyl, carbamyl, halogen, amino, nitro, cyano, hydroxy, C₃₋₁₀ heterocycle containing O, S(O)_(m) and/or NR₁₈ hetero atoms, C₆₋₁₂ aryl, aralkyl or alkaryl, ##STR97## YR₁₅, or NR₁₆ R₁₇ ; X is O, S(O)_(m) , NR₁₉ or CR₂₀ R₂₁ ; Y is O or S(O)_(m) or NR₂₂ ; R₈₋₁₇ and R₁₉₋₂₂ are hydrogen or one of said R₄ members; m is 0-2; and n is 1 to
 5. 2. Compounds according to Formula II ##STR98## and agriculturally acceptable salts and hydrates thereof wherein R₁ is C₁₋₅ alkyl, alkylthio, alkoxyalkyl, C₂₋₄ alkenyl, benzyl, which members may optionally be substituted with halogen, amino, nitro, cyano, hydroxy groups or ##STR99## R₂, R₃, X, Y, and R₈ are as defined for Formula I; R₅ is halogen or hydrogen; andR₆ and R₇ are independently an R₄ member as defined for Formula I.
 3. Compounds according to Formula III: ##STR100## and agriculturally acceptable salts and hydrates thereof wherein R₁ is C₁₋₅ alkyl;R₂, R₃, R₁₀, and Y are as defined for Formula I; R₅ and R₇ are as defined for Formula II; and R₆ is halogen, nitro, cyano, or YR₁₀.
 4. Compounds, salts and hydrates according to claim 3 whereinR₁ is methyl; R₂ is CF₃, CF₂ Cl or CF₂ H; R₃ is chloro or bromo; R₅ is fluoro; R₆ is chloro; and R₇ is propargyloxy, allyloxy, polyalkoxy, OCH(R₂₃)COR₂₄ where R₂₃ is hydrogen, methyl or ethyl, R₂₄ is YR₁₀ or NR₁₁ R₁₂, and Y, R₁₀ -R₁₂ and R₁₈ are as defined for Formula I.
 5. Compound according to claim 3 selected from the group consisting of:4-Chloro-3-(4-chloro-2-fluoro-5-progargyloxyphenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole, 2-(2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorophenoxy)propanoic acid, ethyl ester, (2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorophenoxy)acetic acid, 1-methylethyl ester, 4-Chloro-3-(4-chloro-2-fluoro-5-(methoxymethoxy)phenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole, 4-Chloro-3-(4-chloro-2-fluoro-5-(methoxyethoxy)phenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole, (2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorophenoxy)acetic acid, 1,1-dimethylethyl ester, (2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorophenoxy)acetic acid, 2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorobenzoic acid, 2-ethoxy-1-methyl-2-oxoethyl ester, 2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorobenzoic acid, 2-methoxy-1-methyl-2-oxoethyl ester, 2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorobenzoic acid, ethyl ester, and 2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorobenzoic acid, 1-methylethyl ester.
 6. 4-Chloro-3-(4-chloro-2-fluoro-5-propargyloxyphenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole.
 7. (2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorophenoxy)acetic acid, 1-methylethyl ester.
 8. 2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorobenzoic acid, 2-methoxy-1-methyl-2-oxoethyl ester.
 9. 2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorobenzoic acid, 1methylethyl ester.
 10. Compound according to claim 3 whereinR₁ is methyl; R₂ is CF₃ ; R₃ is chloro or bromo; R₅ is fluoro; R₆ is chloro; and R₇ is ##STR101## wherein X is O, Y is O, and R₁₃ is C₁₋₃ alkyl.
 11. Compound according to claim 10 wherein R₃ is bromo and R₁₃ is isopropyl.
 12. Herbicidal composition comprising an adjuvant and a herbicidally effective amount of a compound according to Formula I: ##STR102## and agriculturally acceptable salts and hydrates thereof wherein R₁ is independently C₁₋₈ alkyl; C₃₋₈ cycloalkyl, cycloalkenyl, cycloalkylalkyl, or cycloalkenylalkyl; C₂₋₈ alkenyl or alkynyl; benzyl; or said R₁ members substituted with halogen, amino, nitro, cyano, hydroxy, alkoxy, alkylthio, ##STR103## YR₁₀, or NR₁₁ R₁₂ ; R₂ is C₁₋₅ haloalkyl;R₃ is halogen; R₄ is an R₁ member, alkylthio, alkoxyalkyl or polyalkoxyalkyl, carbamyl, halogen, amino, nitro, cyano, hydroxy,C₃₋₁₀ heterocycle containing O, S(O)_(m) and/or NR₁₈ hetero atoms, C₆₋₁₂ aryl, aralkyl or alkaryl, ##STR104## YR₁₅, or NR₁₆ R₁₇ group; X is O, S(O)_(m) , NR₁₉ or CR₂₀ R₁₄ ; Y is O or S(O)_(m) or NR₂₂ ; R₈₋₁₇ and R₁₉₋₂₂ are hydrogen or one of said R₄ members; m is 0-2; and n is 1 to
 5. 13. Herbicidal composition comprising an adjuvant and a herbicidally effective amount of a compound according to Formula II: ##STR105## and agriculturally acceptable salts and hydrates thereof wherein R₁ is C₁₋₅ alkyl, alkylthio, alkoxyalkyl, C₂₋₄ alkenyl, benzyl, which members may optionally be substituted with halogen, amino, nitro, cyano, hydroxy groups or ##STR106## R₂, R₃, X, Y, and R₈ are as defined for Formula I; R₅ is halogen or hydrogen; andR₆ and R₇ are independently an R₄ member as defined for Formula I.
 14. Herbicidal composition comprising an adjuvant and a herbicidally-effective amount of a compound according to Formula III: ##STR107## and agriculturally acceptable salts and hydrates thereof wherein R₁ is C₁₋₅ alkyl;R₂, R₃, R₁₀, and Y are as defined for Formula I; R₅ and R₇ are as defined for Formula II; and R₆ is halogen, nitro, cyano, or YR₁₀.
 15. Composition according to claim 13 wherein in Formula IIIR₁ is methyl; R₂ is CF₃, CF₂ Cl or CF₂ H; R₃ is chloro or bromo; R₅ is fluoro; R₆ is chloro; R₇ is propargyloxy, allyloxy, polyalkoxy, OCH(R₂₃)COR₂₄, wherein R₂₃ is hydrogen, methyl or ethyl, R₂₄ is YR₁₀ or NR₁₁ R₁₂, and Y, R₁₀ -R₁₂ and R₁₈ are as defined for Formula I.
 16. Composition comprising an inert adjuvant and a herbicidally-effective amount of 4-Chloro-3-(4-chloro-2-fluoro-5-propargyloxyphenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole.
 17. Composition comprising an inert adjuvant and a herbicidally-effective amount of (2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluoro-phenoxy)acetic acid, 1-methylethyl ester.
 18. Composition comprising an inert adjuvant and a herbicidally-effective amount of 2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorobenzoic acid, 2-methoxy-1-methyl-2-oxoethyl ester.
 19. Composition comprising an inert adjuvant and a herbicidally-effective amount of 2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorobenzoic acid, 1-methylethyl ester.
 20. Composition according to claim 14 wherein said compound is selected from the group consisting of4-Chloro-3-(4-chloro-2-fluoro-5-progargyloxyphenyl)-1-methyl-5-(trifluoromethyl)1H-pyrazole, 2-(2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorophenoxy)propanoic acid, ethyl ester, (2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorophenoxy)acetic acid, 1-methylethyl ester, 4-Chloro-3-(4-chloro-2-fluoro-5-(methoxymethoxy)phenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole, 4-Chloro-3-(4-chloro-2-fluoro-5-(methoxyethoxy)phenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole, (2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorophenoxy)acetic acid, 1,1-dimethylethyl ester, (2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorophenoxy)acetic acid, 2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorobenzoic acid, 2-ethoxy-1-methyl-2-oxoethyl ester, 2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorobenzoic acid, 2-methoxy-1-methyl-2-oxoethyl ester, 2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorobenzoic acid, ethyl ester, and 2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorobenzoic acid, 1-methylethyl ester.
 21. Composition according to claim 14 whereinR₁ is methyl; R₂ is CF₃ ; R₃ is chloro or bromo; R₅ is fluoro; R₆ is chloro; and R₇ is ##STR108## wherein X is O, Y is O, and R₁₃ is C₁₋₃ alkyl.
 22. Composition according to claim 21 wherein R₃ is bromo and R₁₃ is isopropyl.
 23. Method for combatting undesirable plants in crops which comprises applying to the locus thereof a herbicidally effective amount of a compound according to Formula I ##STR109## and agriculturally acceptable salts and hydrates thereof wherein R₁ is independently C₁₋₈ alkyl; C₃₋₈ cycloalkyl, cycloalkenyl, cycloalkylalkyl, or cycloalkenylalkyl; C₂₋₈ alkenyl or alkynyl; benzyl; or said R₁ members substituted with halogen, amino, nitro, cyano, hydroxy, alkoxy, alkylthio, ##STR110## YR₁₀, or NR₁₁ R₁₂ ; R₂ is C₁₋₅ haloalkyl;R₃ is halogen; R₄ is an R₁ member, thioalkyl, alkoxyalkyl or polyalkoxyalkyl, carbamyl, halogen, amino, nitro, cyano, hydroxy, C₃₋₁₀ heterocycle containing O, S(O)_(m) and/or NR₁₈ hetero atoms, C₆₋₁₂ aryl, aralkyl or alkaryl, ##STR111## YR₁₅, or NR₁₆ R₁₇ group; X is 0, S(O)_(m) , NR₁₉ or CR₂₀ R₂₁ ; Y is 0 or S(O)_(m) or NR₂₂ ; R₈₋₁₇ and R₁₉₋₂₂ are hydrogen or one of said R₄ members; m is 0-2; and n is 1 to
 5. 24. Method for combatting undesirable plants in crops which comprises applying to the locus thereof a herbicidally effective amount of a compound according to Formula II ##STR112## and agriculturally acceptable salts and hydrates thereof wherein R₁ is C₁₋₅ alkyl, alkylthio, alkoxyalkyl, C₂₋₄ alkenyl, benzyl, which members may optionally be substituted with halogen, amino, nitro, cyano, hydroxy groups or ##STR113## R₂, R₃, X, Y, and R₈ are as defined for Formula I; R₅ is halogen or hydrogen; andR₆ and R₇ are independently an R₄ member as defined for Formula I.
 25. Method for combatting undesirable plants in crops which comprises applying to the locus thereof a herbicidally effective amount of a compound according to Formula III: ##STR114## and agriculturally acceptable salts and hydrates thereof wherein R₁ is C₁₋₅ alkyl;R₂, R₃, R₁₀, and Y are as defined for Formula I; R₅ and R₇ are as defined for Formula II; and R₆ is halogen, nitro, cyano, or YR₁₀.
 26. Method according to claim 25 whereinR₁ is methyl; R₂ is CF₃, CF₂ Cl or CF₂ H; R₃ is chloro or bromo; R₅ is fluoro; R₆ is chloro; and R₇ is propargyloxy, allyloxy, polyalkoxy, OCH(R₂₃)COR₂₄ where R₂₃ is hydrogen, methyl or ethyl, R₂₄ is YR₁₀ or NR₁₁ R₁₂, and Y, R₁₀ -R₁₂, and R₁₈ are as defined for Formula I.
 27. Method according to claim 25 selected from the group consisting of:4-Chloro-3-(4-chloro-2-fluoro-5-progargyloxyphenyl)-1-methyl-5-(trifluoromethyl)1H-pyrazole, 2-(2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorophenoxy)propanoic acid, ethyl ester, (2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorophenoxy)acetic acid, 1-methylethyl ester, 4-Chloro-3-(4-chloro-2-fluoro-5-(methoxymethoxy)phenyl)-1-methyl-5-(trifluoromethyl)1H-pyrazole, 4-Chloro-3-(4-chloro-2-fluoro-5-(methoxyethoxy)phenyl)-1-methyl-5-(trifluoromethyl)-1H-pyrazole, (2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorophenoxy)acetic acid, 1,1-dimethylethyl ester, (2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorophenoxy)acetic acid, 2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorobenzoic acid, 2-ethoxy-1-methyl-2-oxoethyl ester, 2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorobenzoic acid, 2-methoxy-1-methyl-2-oxoethyl ester, 2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorobenzoic acid, ethyl ester, and 2-Chloro-5-(4-chloro-1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl)-4-fluorobenzoic acid, 1-methylethyl ester.
 28. Method according to claim 25 whereinR₁ is methyl; R₂ is CF₃ ; R₃ is chloro or bromo; R₅ is fluoro; R₆ is chloro; and R₇ is ##STR115## wherein X is O, Y is O, and R₁₃ is C₁₋₃ alkyl.
 29. Compound according to claim 28 wherein R₃ is bromo and R₁₃ is isopropyl. 